Pyrazolyl-substituted heterocycles and their use as phytosanitary products

ABSTRACT

The present invention relates to novel pyrazolyl-substituted heterocycles of the formula (I)  
                 
in which X, Y, Z and Het are as defined in the disclosure, to processes for their preparation, and to their use as pesticides, microbicides and herbicides.

The present invention relates to novel pyrazolyl-substitutedheterocycles, to a plurality of processes for their preparation and totheir use as pesticides, microbicides and herbicides.

Thiophene derivatives described in DE-A-195 27 190 are known to haveinsecticidal and herbicidal properties.

The present invention now provides novel compounds of the formula (I)

in which

-   -   X represents in each case optionally substituted phenyl or        hetaryl,    -   Y represents hydrogen or alkyl,    -   Z represents alkyl, halogen, hydroxyl, alkoxy, haloalkoxy,        optionally substituted phenylalkyloxy, hetarylalkyloxy or        cycloalkyl,    -   Het represents one of the groups        -   in which        -   A represents hydrogen, in each case optionally            halogen-substituted alkyl, alkenyl, alkoxyalkyl,            polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated,            optionally substituted cycloalkyl in which optionally at            least one ring atom is replaced by a heteroatom or            represents in each case optionally halogen-, alkyl-,            haloalkyl-, alkoxy-, haloalkoxy-, cyano- or            nitro-substituted aryl, arylalkyl or hetaryl,        -   B represents hydrogen, alkyl or alkoxyalkyl, or        -   A and B together with the carbon atom to which they are            attached represent a saturated or unsaturated, unsubstituted            or substituted cycle which optionally contains at least one            heteroatom,        -   D represents hydrogen or an optionally substituted radical            from the group consisting of alkyl, alkenyl, alkynyl,            alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or            unsaturated cycloalkyl in which optionally one or more ring            atoms are replaced by heteroatoms, arylalkyl, aryl,            hetarylalkyl and hetaryl, or        -   A and D together with the atoms to which they are attached            represent a saturated or unsaturated cycle which is            unsubstituted or substituted in the A,D moiety and            optionally contains at least one heteroatom,            -   G represents hydrogen (a) or represents one of the                groups            -   in which            -   E represents a metal ion equivalent or an ammonium ion,            -   L represents oxygen or sulphur,            -   M represents oxygen or sulphur,            -   R¹ represents in each case optionally                halogen-substituted alkyl, alkenyl, alkoxyalkyl,                alkylthioalkyl, polyalkoxyalkyl or optionally halogen-,                alkyl- or alkoxy-substituted cycloalkyl which may be                interrupted by at least one heteroatom, represents in                each case optionally substituted phenyl, phenylalkyl,                hetaryl, phenoxyalkyl or hetaryloxyalkyl,            -   R² represents in each case optionally                halogen-substituted alkyl, alkenyl, alkoxyalkyl,                polyalkoxyalkyl or represents in each case optionally                substituted cycloalkyl, phenyl or benzyl,            -   R³ represents alkyl, haloalkyl or represents optionally                substituted phenyl or benzyl,            -   R⁴ and R⁵ independently of one another represent in each                case optionally halogen-substituted alkyl, alkoxy,                alkylamino, dialkylamino, alkylthio, alkenylthio,                cycloalkylthio or represent in each case optionally                substituted phenyl, benzyl, phenoxy or phenylthio,            -   R⁶ and R⁷ independently of one another represent                hydrogen, in each case optionally halogen-substituted                alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl,                represent optionally substituted phenyl, represent                optionally substituted benzyl, or together with the N                atom to which they are attached represent a cycle which                is optionally interrupted by oxygen or sulphur.

Depending inter alia on the nature of the substituents, the compounds ofthe formula (I) can be present as geometrical and/or optical isomers orisomer mixtures of varying composition which, if desired, can beseparated in a customary manner. The present invention provides both thepure isomers and the isomer mixtures, their preparation and their use,and also compositions comprising them. However, hereinbelow, for thesake of simplicity, only compounds of the formula (I) are referred to,although this is meant to be understood as including both the purecompounds and, if appropriate, mixtures with varying proportions ofisomeric compounds.

Including the meanings (1) to (3) of group Het, the following principalstructures (I-1) to (I-3) result:

in which

A, B, D, G, X, Y and Z are as defined above.

Including the principal structures (I-1) to (I-3) and taking intoaccount the possible points of attachment at the pyrazolyl radical, thefollowing principal structures (I-1-A) to (I-3-B) result:

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) ofgroup G, the following principal structures (I-1-A-a) to (I-1-A-g)result if Het represents the group (1)

in which

A, B, D, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as definedabove.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) ofgroup G, the following principal structures (I-1-B-a) to (I-1-B-g)result if Het represents the group (1)

in which

A, B, D, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as definedabove.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) ofgroup G, the following principal structures (I-2-A-a) to (I-2-A-g)result if Het represents the group (2)

in which

A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as definedabove.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) ofgroup G, the following principal structures (I-2-B-a) to (I-2-B-g)result if Het represents the group (2)

in which

A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as definedabove.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) ofgroup G, the following principal structures (I-3-A-a) to (I-3-A-g)result if Het represents the group (3)

in which

A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as definedabove.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) ofgroup G, the following principal structures (I-3-B-a) to (I-3-B-g)result if Het represents the group (3)

in which

A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are as definedabove.

Furthermore, it has been found that the novel compounds of the formula(I) are obtained by one of the processes described below:

-   -   (A) Substituted 3-pyrazolylpyrrolidine-2,4-diones and enols        thereof of the formulae (I-1-A-a) and (I-1-B-a)        -   in which        -   A, B, D, X, Y and Z are as defined above        -   are obtained when        -   N-acylamino acid esters of the formulae (II-A) and (II-B)        -   in which        -   A, B, D, X, Y and Z are as defined above        -   and        -   R⁸ represents alkyl (preferably C₁-C₆-alkyl)        -   are condensed intramolecularly in the presence of a diluent            and in the presence of a base.    -   (B) Furthermore, it has been found that substituted        3-pyrazolyl-4-hydroxy-Δ³-dihydrofuranone derivatives of the        formulae (I-2-A-a) and (I-2-B-a)        -   in which        -   A, B, X, Y and Z are as defined above        -   are obtained when        -   carboxylic acid esters of the formulae (III-A) and (III-B)        -   in which        -   A, B, X, Y, Z and R⁸ are as defined above        -   are condensed intramolecularly in the presence of a diluent            and in the presence of a base.    -   (C) Furthermore, it has been found that substituted        3-thiazolyl-4-hydroxy-Δ³-dihydrothiophen-2-one derivatives of        the formulae (I-3-A-a) and (I-3-B-a)        -   in which        -   A, B, X, Y and Z are as defined above        -   are obtained when        -   β-ketocarboxylic acid esters of the formulae (IV-A) and            (IV-B)        -   in which        -   A, B, X, Y, Z and R⁸ are as defined above and        -   W¹ represents hydrogen, halogen, alkyl (preferably            C₁-C₆-alkyl) or alkoxy (preferably C₁-C₈-alkoxy)        -   are cyclized intramolecularly, if appropriate in the            presence of a diluent and in the presence of a base.

Moreover, it has been found

-   -   (D) that compounds of the formulae (I-1-A-b) to (I-3-B-b) shown        above in which A, B, D, R¹, X, Y and Z are as defined above are        obtained when compounds of the formulae (I-1-A-a) to (I-3-B-a)        shown above in which A, B, D, X, Y and Z are as defined above        are in each case reacted    -   (α) with acid halides of the formula (V)        -   in which        -   R¹ is as defined above and        -   Hal represents halogen (in particular chlorine or bromine)        -   or    -   (β) with carboxylic anhydrides of the formula (VI)        R¹—CO—O—CO—R¹   (VI)    -   in which    -   R¹ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder;    -   (E) that the compounds of the formulae (I-1-A-c) to (I-3-B-c)        shown above in which A, B, D, R², M, X, Y and Z are as defined        above and L represents oxygen are obtained when compounds of the        formulae (I-1-A-a) to (I-3-B-a) shown above in which A, B, D, X,        Y and Z are as defined above are in each case reacted        -   with chloroformic acid esters or chloroformic acid            thioesters of the formula (VII)            R²-M-CO—Cl   (VII)    -   in which    -   R² and M are as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder;    -   (F) that compounds of the formulae (I-1-A-c) to (I-3-B-c) shown        above in which A, B, D, R², M, X, Y and Z are as defined above        and L represents sulphur are obtained when compounds of the        formulae (I-1-A-a) to (I-3-B-a) shown above in which A, B, D, X,        Y and Z are as defined above are in each case reacted        -   with chloromonothioformic acid esters or chlordithioformic            acid esters of the formula (VII)        -   in which        -   M and R² are as defined above,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid binder        -   and    -   (G) that compounds of the formulae (I-1-A-d) to (I-3-B-d) shown        above in which A, B, D, R³, X, Y and Z are as defined above are        obtained when compounds of the formulae (I-1-A-a) to (I-3-B-a)        shown above in which A, B, D, X, Y and Z are as defined above        are in each case reacted        -   with sulphonyl chlorides of the formula (IX)            R³—SO₂—Cl   (IX)    -   in which    -   R³ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of an acid binder,    -   (H) that compounds of the formulae (I-1-A-e) to (I-3-B-e) shown        above in which A, B, D, L, R⁴, R⁵, X, Y and Z are as defined        above are obtained when compounds of the formulae (I-1-A-a) to        (I-3-B-a) shown above in which A, B, D, X, Y and Z are as        defined above are in each case reacted        -   with phosphorus compounds of the formula (X)        -   in which        -   L, R⁴ and R⁵ are as defined above and        -   Hal represents halogen (in particular chlorine or bromine),        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid binder,    -   (I) that compounds of the formulae (I-1-A-f) to (I-3-B-f) shown        above in which A, B, D, E, X, Y and Z are as defined above are        obtained when compounds of the formulae (I-1-A-a) to (I-3-B-a)        shown above in which A, B, D, X, Y and Z are as defined above        are in each case reacted        -   with metal compounds or amines of the formulae (XI) or            (XII), respectively,            Me(OR¹⁰)_(t)   (XI)    -   in which    -   Me represents a mono- or divalent metal (preferably an alkali        metal or alkaline earth metal such as lithium, sodium,        potassium, magnesium or calcium),    -   t represents the number 1 or 2 and    -   R¹⁰, R¹¹, R¹² independently of one another represent hydrogen or        alkyl (preferably C₁-C₈-alkyl),    -   if appropriate in the presence of a diluent,    -   (J) that compounds of the formulae (I-1-A-g) to (I-3-B-g) shown        above in which A, B, D, L, R⁶, R⁷, X, Y and Z are as defined        above are obtained when compounds of the formulae (I-1-A-a) to        (I-3-B-a) shown above in which A, B, D, X, Y and Z are as        defined above are in each case reacted    -   (α) with isocyanates or isothiocyanates of the formula (XIII)        R⁶—N═C═L   (XIII)    -   in which    -   R⁶ and L are as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a catalyst, or    -   (β) with carbamoyl chlorides or thiocarbamoyl chlorides of the        formula (XIV)        -   in which        -   L, R⁶ and R⁷ are as defined above,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid binder.

Furthermore, it has been found that the novel compounds of the formula(I) are highly active as pesticides, preferably as insecticides andacaricides, and as herbicides.

The formula (I) provides a general definition of the compounds accordingto the invention. Preferred substituents or ranges of the radicalslisted in the formulae mentioned above and below are illustrated below,

where the points of attachment are in accordance with structures I-1-Ato I-3-B:

-   -   X preferably represents in each case optionally halogen-,        C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₄-haloalkyl-,        C₁-C₄-haloalkoxy-, nitro- or cyano-substituted phenyl or 5- or        6-membered hetaryl,    -   Y preferably represents hydrogen, halogen or C₁-C₆-alkyl,    -   Z preferably represents C₁-C₆-alkyl, halogen, hydroxyl,        C₁-C₆-alkoxy, C₁-C₆-haloalkoxy or in each case optionally        C₁-C₆-alkyl-, C₁-C₆-alkoxy-, halogen-, C₁-C₄-haloalkyl-,        C₁-C₆-haloalkoxy-, cyano- or nitro-substituted        phenyl-C₁-C₂-alkoxy or hetaryl-C₁-C₂-alkoxy or optionally        C₁-C₂-alkyl- or halogen-substituted C₃-C₆-cycloalkyl,    -   Het preferably represents one of the groups    -   A preferably represents hydrogen or in each case optionally        fluorine- or chlorine-substituted C₁-C₁ 2-alkyl, C₃-C₈-alkenyl,        C₁-C₁₀-alkoxy-C₁-C₈-alkyl, poly-C₁-C₈-alkoxy-C₁-C₈-alkyl,        C₁-C₁₀-alkylthio-C₁-C₆-alkyl, optionally fluorine-, chlorine-,        C₁-C₆-alkyl- or C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl in        which optionally one or two not directly adjacent ring members        are replaced by oxygen and/or sulphur or represents in each case        optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-haloalkyl-,        C₁-C₆-alkoxy-, C₁-C₆-haloalkoxy-, cyano- or nitro-substituted        C₆- or C₁₀-aryl (phenyl or naphthyl), hetaryl having 5 or 6 ring        atoms (for example furanyl, pyridyl, imidazolyl, triazolyl,        pyrazolyl, pyrimidyl, thiazolyl or thienyl) or C₆- or        C₁₀-aryl-C₁-C₆-alkyl (phenyl-C₁-C₆-alkyl or        naphthyl-C₁-C₆-alkyl),    -   B preferably represents hydrogen, C₁-C₁₂-alkyl or        C₁-C₈-alkoxy-C₁-C₆-alkyl, or    -   A, B and the carbon atom to which they are attached preferably        represent saturated C₃-C₁₀-cycloalkyl or unsaturated        C₅-C₁₀-cycloalkyl in which optionally one ring member is        replaced by oxygen or sulphur and which are optionally mono- or        disubstituted by C₁-C₈-alkyl, C₃-C₁₀-cycloalkyl,        C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen or        phenyl, or    -   A, B and the carbon atom to which they are attached preferably        represent C₅-C₆-cycloalkyl which is substituted by an        alkylenediyl group which optionally contains one or two not        directly adjacent oxygen and/or sulphur atoms or by an        alkylenedioxyl or an alkylenedithioyl group which, together with        the carbon atom to which it is attached, forms a further five-        to eight-membered ring which may optionally be substituted by        C₁-C₄-alkyl, or    -   A, B and the carbon atom to which they are attached preferably        represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which two        substituents together with the carbon atoms to which they are        attached represent in each case optionally C₁-C₆-alkyl-,        C₁-C₆-alkoxy- or halogen-substituted C₂-C₆-alkanediyl,        C₂-C₆-alkenediyl or C₄-C₆-alkanedienediyl in which optionally        one methylene group is replaced by oxygen or sulphur,    -   D preferably represents hydrogen, in each case optionally        halogen-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl,        C₁-C₁₀-alkoxy-C₂-C₈-alkyl, poly-C₁-C₈-alkoxy-C₂-C₈-alkyl,        C₁-C₁₀-alkylthio-C₂-C₈-alkyl, optionally halogen-, C₁-C₄-alkyl-,        C₁-C₄-alkoxy- or C₁-C₄-haloalkyl-substituted C₃-C₈-cycloalkyl in        which optionally one ring member is replaced by oxygen or        sulphur, or represents in each case optionally halogen-,        C₁-C₆-alkyl-, C₁-C₆-haloalkyl-, C₁-C₆-alkoxy-,        C₁-C₆-haloalkoxy-, cyano- or nitro-substituted phenyl, hetaryl        having 5 or 6 ring atoms (for example furanyl, imidazolyl,        pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl or        triazolyl), phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkyl having 5        or 6 ring atoms (for example furanyl, imidazolyl, pyridyl,        thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl or triazolyl)        or    -   A and D together preferably represent in each case optionally        substituted C₃-C₆-alkanediyl or C₃-C₆-alkenediyl in which        optionally one methylene group is replaced by a carbonyl group,        oxygen or sulphur,        -   possible substituents being in each case:        -   halogen, hydroxyl, mercapto or in each case optionally            halogen-substituted C₁-C₁₀-alkyl, C₁-C₆-alkoxy,            C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, phenyl or benzyloxy, or a            further C₃-C₆-alkanediyl grouping, C₃-C₆-alkenediyl grouping            or a butadienyl grouping which is optionally substituted by            C₁-C₆-alkyl or in which optionally two adjacent substituents            together with the carbon atoms to which they are attached            form a further saturated or unsaturated cycle having 5 or 6            ring atoms (in the case of the compounds of the formula            (I-1), A and D together with the atoms to which the are            attached then represent, for example, the groups AD-1 to            AD-10 mentioned further below), which cycle may contain            oxygen or sulphur,    -   G preferably represents hydrogen (a) or represents one of the        groups        in particular (a), (b), (c) or g),    -   L    -   in which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur,    -   R¹ preferably represents in each case optionally        halogen-substituted C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,        C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl,        poly-C₁-C₈-alkoxy-C₁-C₈-alkyl or optionally halogen-,        C₁-C₆-alkyl- or C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl in        which optionally one or more (preferably not more than two) not        directly adjacent ring members are replaced by oxygen and/or        sulphur,        -   represents optionally halogen-, cyano-, nitro-,            C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₆-haloalkyl-,            C₁-C₆-haloalkoxy-, C₁-C₆-alkylthio- or            C₁-C₆-alkylsulphonyl-substituted phenyl,        -   represents optionally halogen-, nitro-, cyano-,            C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₆-haloalkyl- or            C₁-C₆-haloalkoxy-substituted phenyl-C₁-C₆-alkyl, represents            optionally halogen-, C₁-C₆-alkyl-, C₁-C₂-haloalkyl- or            C₁-C₄-alkoxy-substituted 5- or 6-membered hetaryl (for            example pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or            thienyl),        -   represents optionally halogen- or C₁-C₆-alkyl-substituted            phenoxy-C₁-C₆-alkyl or        -   represents optionally halogen-, amino- or            C₁-C₆-alkyl-substituted 5- or 6-membered            hetaryloxy-C₁-C₆-alkyl (for example pyridyloxy-C₁-C₆-alkyl,            pyrimidyloxy-C₁-C₆-alkyl or thiazolyloxy-C₁-C₆-alkyl),    -   R² preferably represents in each case optionally        halogen-substituted C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,        C₁-C₈-alkoxy-C₂-C₈-alkyl, poly-C₁-C₈-alkoxy-C₂-C₈-alkyl,        -   represents optionally halogen-, C₁-C₆-alkyl- or            C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl in which            optionally one ring atom is replaced by oxygen, or        -   represents in each case optionally halogen-, cyano-, nitro-,            C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₆-haloalkyl- or            C₁-C₆-haloalkoxy-substituted phenyl or benzyl,    -   R³ preferably represents optionally halogen-substituted        C₁-C₈-alkyl or represents in each case optionally halogen-,        C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₄-haloalkyl-,        C₁-C₄-haloalkoxy-, cyano- or nitro-substituted phenyl or benzyl,    -   R⁴ and R⁵ preferably independently of one another represent in        each case optionally halogen-substituted C₁-C₈-alkyl,        C₁-C₈-alkoxy, C₁-C₈-alkylamino, di-(C₁-C₈-alkyl)amino,        C₁-C₈-alkylthio, C₂-C₈-alkenylthio, C₃-C₇-cycloalkylthio or        represent in each case optionally halogen-, nitro-, cyano-,        C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, C₁-C₄-alkylthio-,        C₁-C₄-haloalkylthio-, C₁-C₄-alkyl- or        C₁-C₄-haloalkyl-substituted phenyl, phenoxy or phenylthio,    -   R⁶ and R⁷ independently of one another preferably represent        hydrogen, represent in each case optionally halogen-substituted        C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl,        C₁-C₈-alkoxy-C₁-C₈-alkyl, represent optionally halogen-,        C₁-C₈-haloalkyl-, C₁-C₈-alkyl- or C₁-C₈-alkoxy-substituted        phenyl, optionally halogen-, C₁-C₈-alkyl-, C₁-C₈-haloalkyl- or        C₁-C₈-alkoxy-substituted benzyl or together represent an        optionally C₁-C₄-alkyl-substituted C₃-C₆-alkylene radical in        which optionally one carbon atom is replaced by oxygen or        sulphur.

In the radical definitions mentioned as being preferred, halogenrepresents fluorine, chlorine, bromine or iodine, in particularfluorine, chlorine and bromine.

-   -   X particularly preferably represents phenyl, pyridyl, pyrimidyl        or thiazolyl, each of which is optionally mono- to        trisubstituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,        C₁-C₄-alkoxy, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, nitro or cyano,    -   Y particularly preferably represents hydrogen, chlorine, bromine        or C₁-C₄-alkyl,    -   Z particularly preferably represents C₁-C₄-alkyl, chlorine,        bromine, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy or represents benzyloxy        or hetaryloxy having 5 or 6 ring atoms (for example furanyl,        pyridyl, pyrimidyl, thiazolyl, thienyl), each of which radicals        is optionally mono- or disubstituted by C₁-C₄-alkyl,        C₁-C₄-alkoxy, fluorine, chlorine, bromine, C₁-C₂-haloalkyl,        C₁-C₂-haloalkoxy, cyano or nitro,    -   Het particularly preferably represents one of the groups    -   A particularly preferably represents hydrogen, in each case        optionally fluorine-substituted C₁-C₁₀-alkyl,        C₁-C₈-alkoxy-C₁-C₆-alkyl, optionally fluorine-, chlorine-,        C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted C₃-C₇-cycloalkyl in        which optionally one ring member is replaced by oxygen or        sulphur or represents phenyl or phenyl-C₁-C₂-alkyl, each of        which is optionally substituted by fluorine, chlorine, bromine,        C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, cyano, nitro or        C₁-C₄-haloalkoxy,    -   B particularly preferably represents hydrogen or C₁-C₁₀-alkyl or    -   A, B and the carbon atom to which they are attached particularly        preferably represent saturated C₃-C₇-cycloalkyl or unsaturated        C₅-C₇-cycloalkyl in which optionally one ring member is replaced        by oxygen or sulphur and which is optionally mono- or        disubstituted by C₁-C₆-alkyl, C₅-C₈-cycloalkyl, C₁-C₃-haloalkyl,        C₁-C₆-alkoxy, fluorine, chlorine or phenyl, or    -   A, B and the carbon atom to which they are attached particularly        preferably represent C₅-C₆-cycloalkyl which is substituted by an        alkylenediyl group which optionally contains one or two not        directly adjacent oxygen or sulphur atoms or by an        alkylenedioxyl or by an alkylenedithiolyl group which, together        with the carbon atom to which it is attached, forms a further        five- or six-membered ring which may optionally be substituted        by C₁-C₃-alkyl, or    -   A, B and the carbon atom to which they are attached particularly        preferably represent C₅-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in        which two substituents together with the carbon atoms to which        they are attached represent C₂-C₄-alkanediyl, C₂-C₄-alkenediyl        in which optionally one methylene group is replaced by oxygen or        sulphur, each of which radicals is optionally substituted by        C₁-C₅-alkyl, C₁-C₅-alkoxy, fluorine, chlorine or bromine, or        represent butadienediyl,    -   D particularly preferably represents hydrogen, represents in        each case optionally fluorine-substituted C₁-C₁₀-alkyl,        C₃-C₆-alkenyl, C₁-C₆-alkoxy-C₂-C₄-alkyl or        C₁-C₆-alkylthio-C₂-C₄-alkyl, represents optionally fluorine-,        C₁-C₄-alkyl-, C₁-C₄-alkoxy- or C₁-C₂-haloalkyl-substituted        C₃-C₇-cycloalkyl in which optionally one methylene group is        replaced by oxygen or sulphur or represents phenyl or        phenyl-C₁-C₄-alkyl, each of which is optionally substituted by        fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₁-C₄-akoxy or C₁-C₄-haloalkoxy, or    -   A and D together particularly preferably represent optionally        substituted C₃-C₅-alkanediyl in which optionally one methylene        group may be replaced by oxygen or sulphur, possible        substituents being C₁-C₆-alkyl and C₁-C₄-alkoxy, or    -   A and D represent (in the case of compounds of the formula        (I-1)), together with the atoms to which they are attached, one        of the groups AD-1 to AD-10:    -   G particularly preferably represents hydrogen (a) or represents        one of the groups        in particular (a), (b), (c) or (g),    -   in which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur,    -   R¹ particularly preferably represents in each case optionally        fluorine- or chlorine-substituted C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl,        C₁-C₆-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkylthio-C₁-C₄-alkyl or        optionally fluorine-, chlorine-, C₁-C₅-alkyl- or        C₁-C₅-alkoxy-substituted C₃-C₇-cycloalkyl in which optionally        one or two not directly adjacent ring members are replaced by        oxygen and/or sulphur,        -   represents optionally fluorine-, chlorine-, bromine-,            cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-,            C₁-C₃-haloalkyl-, C₁-C₃-haloalkoxy-, C₁-C₄-alkylthio- or            C₁-C₄-alkylsulphonyl-substituted phenyl,        -   represents optionally fluorine-, chlorine-, bromine-,            C₁-C₄-alkyl-, C₁-C₄-alkoxy-, C₁-C₃-haloalkyl- or            C₁-C₃-haloalkoxy-substituted phenyl-C₁-C₄-alkyl,        -   represents in each case optionally fluorine-, chlorine-,            bromine-, C₁-C₄-alkyl-, trifluoromethyl- or            C₁-C₂-alkoxy-substituted pyrazolyl, thiazolyl, pyridyl,            pyrimidyl, furanyl or thienyl,    -   R² particularly preferably represents in each case optionally        fluorine-substituted C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl or        C₁-C₆-alkoxy-C₂-C₆-alkyl,        -   represents optionally fluorine-, chlorine-, C₁-C₄-alkyl- or            C₁-C₄-alkoxy-substituted C₃-C₇-cycloalkyl or        -   represents in each case optionally fluorine-, chlorine-,            bromine-, cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₃-alkoxy-,            C₁-C₂-haloalkyl- or C₁-C₂-haloalkoxy-substituted phenyl or            benzyl,    -   R³ particularly preferably represents optionally        fluorine-substituted C₁-C₆-alkyl or represents in each case        optionally fluorine-, chlorine-, bromine-, C₁-C₄-alkyl-,        C₁-C₄-alkoxy-, C₁-C₃-haloalkyl-, C₁-C₃-haloalkoxy-, cyano- or        nitro-substituted phenyl,    -   R⁴ particularly preferably represents C₁-C₆-alkyl, C₁-C₆-alkoxy,        C₁-C₆-alkylamino, di-(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio,        C₃-C₄-alkenylthio, C₃-C₆-cycloalkylthio or represents in each        case optionally fluorine-, chlorine-, bromine-, nitro-, cyano-,        C₁-C₃-alkoxy-, C₁-C₃-haloalkoxy-, C₁-C₃-alkylthio-,        C₁-C₃-haloalkylthio-, C₁-C₃-alkyl- or        C₁-C₃-haloalkyl-substituted phenyl, phenoxy or phenylthio,    -   R⁵ particularly preferably represents C₁-C₆-alkoxy or        C₁-C₆-alkylthio,    -   R⁶ particularly preferably represents C₁-C₆-alkyl,        C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl,        C₁-C₆-alkoxy-C₁-C₆-alkyl, represents optionally fluorine-,        chlorine-, bromine-, C₁-C₃-haloalkyl-, C₁-C₄-alkyl- or        C₁-C₄-alkoxy-substituted phenyl, represents optionally        fluorine-, chlorine-, bromine-, C₁-C₄-alkyl-, C₁-C₃-haloalkyl-        or C₁-C₄-alkoxy-substituted benzyl,    -   R⁷ particularly preferably represents hydrogen, C₁-C₆-alkyl,        C₃-C₆-alkenyl,    -   R⁶ and R⁷ particularly preferably together represent an        optionally methyl- or ethyl-substituted C₄-C₅-alkylene radical        in which optionally one methylene group is replaced by oxygen or        sulphur.

In the radical definitions mentioned as being particularly preferred,halogen represents fluorine, chlorine, bromine and iodine, in particularfluorine, chlorine and bromine.

-   -   X very particularly preferably represents phenyl which is        optionally mono- or disubstituted by fluorine, chlorine,        bromine, methyl, ethyl, trifluoromethyl, isopropyl, tert-butyl,        trifluoromethoxy, methoxy, ethoxy, isopropoxy, tert-butoxy,        cyano or nitro,    -   Y very particularly preferably represents hydrogen, methyl or        ethyl,    -   Z very particularly preferably represents methyl, ethyl, propyl,        isopropyl, chlorine, methoxy, ethoxy, propoxy, isopropoxy,        difluoromethoxy or trifluoroethoxy,    -   Het very particularly preferably represents one of the groups    -   A very particularly preferably represents hydrogen, represents        in each case optionally fluorine-substituted C₁-C₈-alkyl or        C₁-C₆-alkoxy-C₁-C₄-alkyl, optionally fluorine-, methyl-, ethyl-        or methoxy-substituted C₃-C₆-cycloalkyl in which optionally one        ring member is replaced by oxygen or sulphur, or represents        phenyl or benzyl, each of which is optionally mono- or        disubstituted by fluorine, chlorine, bromine, methyl, ethyl,        n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl,        trifluoromethoxy, cyano or nitro,    -   B very particularly preferably represents hydrogen or        C₁-C₆-alkyl or    -   A, B and the carbon atom to which they are attached very        particularly preferably represent saturated C₃-C₆-cycloalkyl in        which optionally one ring member is replaced by oxygen or        sulphur and which is optionally monosubstituted by methyl,        ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,        tert-butyl, trifluoromethyl, methoxy, ethoxy, propoxy,        isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, fluorine        or chlorine, or    -   A, B and the carbon atom to which they are attached very        particularly preferably represent C₆-cycloalkyl which is        substituted by an alkylenedioxyl group which is optionally mono-        or disubstituted by methyl or ethyl and which, together with the        carbon atom to which it is attached, forms a further five- or        six-membered ring, or    -   A, B and the carbon atom to which they are attached very        particularly preferably represent C₅-C₆-cycloalkyl or        C₅-C₆-cycloalkenyl in which two substituents together with the        carbon atoms to which they are attached represent        C₂-C₄-alkanediyl or C₂-C₄-alkenediyl in which in each case        optionally one methylene group is replaced by oxygen or sulphur,        or represent butadienediyl,    -   D very particularly preferably represents hydrogen, represents        in each case optionally fluorine-substituted C₁-C₈-alkyl,        C₃-C₄-alkenyl, C₁-C₆-alkoxy-C₂-C₄-alkyl,        C₁-C₄-alkylthio-C₂-C₄-alkyl or represents trifluoromethyl- or        fluorine-substituted C₃-C₆-cycloalkyl in which optionally one        methylene group is replaced by oxygen or sulphur or represents        phenyl or benzyl, each of which is optionally mono- or        disubstituted by fluorine, chlorine, methyl, ethyl, n-propyl,        isopropyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,    -   or    -   A and D together very particularly preferably represent        C₃-C₄-alkanediyl in which optionally one carbon atom is replaced        by sulphur and which is optionally mono- or disubstituted by        methyl, ethyl, methoxy or ethoxy, or    -   A and D (in the case of the compounds of the formula (I-1))        together with the atoms to which they are attached represent one        of the groups AD below:    -   G very particularly preferably represents hydrogen (a) or        represents one of the groups        in particular (a), (b) or (c),    -   in which    -   E represents a metal ion equivalent or an ammonium ion,    -   L represents oxygen or sulphur and    -   M represents oxygen or sulphur,    -   R¹ very particularly preferably represents in each case        optionally fluorine- or chlorine-substituted C₁-C₁₄-alkyl,        C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₂-alkyl,        C₁-C₄-alkylthio-C₁-C₂-alkyl or represents C₃-C₆-cycloalkyl which        is optionally mono- or disubstituted by fluorine, chlorine,        methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,        methoxy or ethoxy and in which optionally one or two not        directly adjacent ring members are replaced by oxygen and/or        sulphur,        -   represents phenyl which is optionally mono- or disubstituted            by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl,            n-propyl, i-propyl, tert-butyl, methoxy, ethoxy, i-propoxy,            tert-butoxy, trifluoromethyl or trifluoromethoxy,        -   represents furanyl, thienyl or pyridyl, each of which is            optionally mono- or disubstituted by fluorine, chlorine,            bromine, methyl or ethyl,    -   R² very particularly preferably represents C₁-C₁₄-alkyl,        C₂-C₁₄-alkenyl or C₁-C₄-alkoxy-C₂-C₆-alkyl, each of which is        optionally mono- to trisubstituted by fluorine,        -   represents C₃-C₆-cycloalkyl which is optionally mono- or            disubstituted by fluorine, chlorine, methyl, ethyl,            n-propyl, isopropyl or methoxy,        -   or represents phenyl or benzyl, each of which is optionally            mono- or disubstituted by fluorine, chlorine, cyano, nitro,            methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy,            trifluoromethyl or trifluoromethoxy,    -   R³ very particularly preferably represents methyl, ethyl,        n-propyl, each of which is optionally mono- to trisubstituted by        fluorine or represents phenyl which is optionally mono- or        disubstituted by fluorine, chlorine, bromine, methyl,        tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or        nitro,    -   R⁴ very particularly preferably represents C₁-C₄-alkyl,        C₁-C₄-alkoxy, C₁-C₄-alkylamino, di-(C₁-C₄-alkyl)amino,        C₁-C₄-alkylthio or represents phenyl, phenoxy or phenylthio,        each of which is optionally mono- or disubstituted by fluorine,        chlorine, bromine, nitro, cyano, C₁-C₂-alkoxy,        C₁-C₂-fluoroalkoxy, C₁-C₂-alkylthio, C₁-C₂-fluoroalkylthio or        C₁-C₃-alkyl,    -   R⁵ very particularly preferably represents methoxy, ethoxy,        methylthio or ethylthio,    -   R⁶ very particularly preferably represents C₁-C₄-alkyl,        C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₃-C₄-alkenyl,        C₁-C₄-alkoxy-C₁-C₄-alkyl, represents phenyl which is optionally        mono- or disubstituted by fluorine, chlorine, bromine,        trifluoromethyl, methyl or methoxy, represents benzyl which is        optionally mono- or disubstituted by fluorine, chlorine,        bromine, methyl, trifluoromethyl or methoxy,    -   R⁷ very particularly preferably represents hydrogen, methyl,        ethyl, propyl or allyl,    -   R⁶ and R⁷ very particularly preferably together represent a        C₅-C₆-alkylene radical in which optionally one methylene group        is replaced by oxygen or sulphur.    -   X most preferably represents phenyl which is optionally mono- or        disubstituted by fluorine, chlorine, bromine, methyl,        trifluoromethyl, methoxy or trifluoromethoxy,    -   Y most preferably represents hydrogen or methyl,    -   Z most preferably represents methyl, ethyl or propyl,    -   Het most preferably represents one of the groups    -   A most preferably represents hydrogen or C₁-C₆-alkyl,    -   B most preferably represents hydrogen or C₁-C₆-alkyl or    -   A, B and the carbon atom to which they are attached most        preferably represent saturated C₅-C₆-cycloalkyl in which        optionally one ring member is replaced by oxygen or sulphur and        which is optionally monosubstituted by methyl, ethyl, propyl,        isopropyl, trifluoromethyl, methoxy, ethoxy, propoxy,        isopropoxy, butoxy or isobutoxy, or    -   A, B and the carbon atom to which they are attached most        preferably represent C₅-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in        which two substituents together with the carbon atoms to which        they are attached represent butadienyl,    -   D most preferably represents hydrogen, methyl, ethyl or        isopropyl or represents trifluoromethyl-substituted cyclohexyl,    -   A and D together most preferably represent C₃-C₄-alkanediyl,    -   G most preferably represents hydrogen (a) or represents one of        the groups        -   in which        -   L represents oxygen and        -   M represents oxygen or sulphur,    -   R¹ most preferably represents C₁-C₆-alkyl, C₂-C₆-alkenyl,        C₁-C₂-alkoxy-C₁-C₂-alkyl, C₁-C₂-alkylthio-C₁-C₂-alkyl, each of        which is optionally mono- to trisubstituted by fluorine or        chlorine, or represents C₃-C₆-cycloalkyl which is optionally        monosubstituted by fluorine, chlorine, methyl, ethyl or methoxy        and in which optionally one ring member is replaced by oxygen or        sulphur,        -   represents phenyl which is optionally monosubstituted by            fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl,            n-propyl, i-propyl, tert-butyl, methoxy, ethoxy, i-propoxy,            tert-butoxy, trifluoromethyl or trifluoromethoxy,        -   represents thienyl or pyridyl, each of which is optionally            monosubstituted by fluorine, chlorine, bromine, methyl or            ethyl,    -   R² most preferably represents C₁-C₆-alkyl, C₂-C₆-alkenyl or        C₁-C₄-alkoxy-C₂-C₃-alkyl, each of which is optionally mono- to        trisubstituted by fluorine, represents cyclopentyl or        cyclohexyl,        -   or represents phenyl or benzyl, each of which is optionally            monosubstituted by fluorine, chlorine, cyano, nitro, methyl,            ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl            or trifluoromethoxy.

If the pyrazole radical has the following point of attachment:

then

-   -   X in particular represents phenyl which is optionally mono- or        disubstituted by chlorine, bromine or trifluoromethyl,    -   Y in particular represents hydrogen,    -   Z in particular represents methyl, ethyl or propyl,    -   Het in particular represents one of the groups    -   A in particular represents hydrogen or C₁-C₆-alkyl,    -   B in particular represents hydrogen or C₁-C₆-alkyl,    -   A, B and the carbon atom to which they are attached in        particular represent saturated C₆-cycloalkyl in which optionally        one ring member is replaced by oxygen or in particular represent        saturated C₆-cycloalkyl which is optionally monosubstituted by        methyl, trifluoromethyl, methoxy or ethoxy,    -   A, B and the carbon atom to which they are attached in        particular represent C₅-C₆-cycloalkyl in which two substituents        together with the carbon atoms to which they are attached        represent butadienyl,    -   D in particular represents hydrogen or represents cyclohexyl        which is 20 monosubstituted by trifluoromethyl,    -   A and D in particular represent C₃-C₄-alkanediyl,    -   G in particular represents hydrogen (a) or represents one of the        groups        -   in which        -   R¹ in particular represents C₁-C₆-alkyl, C₃-cycloalkyl,            represents in each case chlorine-substituted phenyl or            pyridyl,        -   R² in particular represents C₁-C₆-alkyl or benzyl.

If the pyrazole radical has the following point of attachment:

then

-   -   X in particular represents phenyl which is monosubstituted by        chlorine or trifluoromethyl,    -   Y in particular represents methyl,    -   Z in particular represents methyl,    -   Het in particular represents the group    -   A in particular represents methyl,    -   B in particular represents methyl,    -   A, B and and the carbon atom to which they are attached in        particular represent C₆-cycloalkyl which is monosubstituted by        methoxy,    -   D in particular represents hydrogen,    -   G in particular represents hydrogen or the group    -   R² in particular represents C₁-C₆-alkyl.

The general or preferred radical definitions or illustrations listedabove can be combined with one another as desired, i.e. includingcombinations between the respective ranges and preferred ranges. Theyapply both to the end products and, correspondingly, to precursors andintermediates.

Preference according to the invention is given to the compounds of theformula (I) which contain a combination of the meanings listed above asbeing preferred (preferable).

Particular preference according to the invention is given to thecompounds of the formula (1) which contain a combination of the meaningslisted above as being particularly preferred.

Very particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

Most preference according to the invention is given to the compounds ofthe formula (I) which contain a combination of the meanings listed aboveas being most preferred.

Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl,can in each case be straight-chain or branched as far as this ispossible, including in combination with heteroatoms, such as, forexample, in alkoxy.

Optionally substituted radicals can, unless stated otherwise, be mono-or polysubstituted, where in the case of polysubstitution thesubstituents can be identical or different.

In addition to the compounds mentioned in the Preparation Examples, thefollowing compounds of the formula (I-1-A-a) may be specificallymentioned. TABLE 1

A B D CH₃ H H C₂H₅ H H C₃H₇ H H i-C₃H₇ H H C₄H₉ H H i-C₄H₉ H H s-C₄H₉ HH t-C₄H₉ H H CH₃ CH₃ H C₂H₅ CH₃ H C₃H₇ CH₃ H i-C₃H₇ CH₃ H C₄H₉ CH₃ Hi-C₄H₉ CH₃ H s-C₄H₉ CH₃ H t-C₄H₉ CH₃ H C₂H₅ C₂H₅ H C₃H₇ C₃H₇ H

CH₃ H

CH₃ H

CH₃ H —(CH₂)₂— H —(CH₂)₂— H —(CH₂)₃— H —(CH₂)₅— H —(CH₂)₆— H —(CH₂)₇— H—(CH₂)₂—O—(CH₂)₂— H —CH₂—O—(CH₂)₃— H —(CH₂)₂—S—(CH₂)₂— H—CH₂—CHCH₃—(CH₂)₃— H —(CH₂)₂—CHCH₃—(CH₂)₂— H —(CH₂)₂—CHC₂H₅—(CH₂)₂— H—(CH₂)₂—CHC₃H₇—(CH₂)₂— H —(CH₂)₂—CH-i-C₃H₇—(CH₂)₂— H—(CH₂)₂—CHOCH₃—(CH₂)₂— H —(CH₂)₂—CHOC₂H₅—(CH₂)₂— H—(CH₂)₂—CHOC₃H₇—(CH₂)₂— H —(CH₂)₂—CHi-OC₃H₇—(CH₂)₂— H—(CH₂)₂—C(CH₃)₂—(CH₂)₂— H —(CH₂)₂—(CHCH₃)₂—(CH₂)₂— H

H

H

H

H

H A D B —(CH₂)₃— H —(CH₂)₄— H —CH₂—CHCH₃—CH₂— H —CH₂—CH₂—CHCH₃— H—CH₂—CHCH₃—CHCH₃— H —CH₂—S—CH₂— H A B D —CH₂—S—(CH₂)₂— H —(CH₂)₂—S—CH₂—H

H H CH₃ H H C₂H₅ H H C₃H₇ H H i-C₃H₇ H H

H H

H H

H CH₃ CH₃ H CH₃ C₂H₅ H A D B CH₃ C₃H₇ H CH₃ i-C₃H₇ H CH₃

H CH₃

H CH₃

H C₂H₅ CH₃ H C₂H₅ C₂H₅ H

TABLE 2 A, B and D are as stated in Table 1 X = 4-Cl—C₆H₄, Z = C₂H₅.

TABLE 3 A, B and D are as stated in Table 1 X = 4-Cl—C₆H₄, Z = C₃H₇.

TABLE 4 A, B and D are as stated in Table 1 X = 3,4-Cl₂—C₆H₃, Z = CH₃.

TABLE 5 A, B and D are as stated in Table 1 X = 3,4-Cl₂—C₆H₃, Z = C₂H₅.

TABLE 6 A, B and D are as stated in Table 1 X = 3,4-Cl₂—C₆H₃, Z = C₃H₇.

TABLE 7 A, B and D are as stated in Table 1 X = 4-CF₃—C₆H₄, Z = CH₃.

TABLE 8 A, B and D are as stated in Table 1 X = 4-CF₃—C₆H₄, Z = C₂H₅.

TABLE 9 A, B and D are as stated in Table 1 X = 4-CF₃—C₆H₄, Z = C₃H₇.

TABLE 10 A, B and D are as stated in Table 1 X = 4-Br—C₆H₄, Z = CH₃.

TABLE 11 A, B and D are as stated in Table 1 X = 4-Br—C₆H₄, Z C₂H₅.

TABLE 12 A, B and D are as stated in Table 1 X = 4-Br—C₆H₄, Z = C₃H₇.

In addition to the compounds mentioned in the Preparation Examples, thefollowing compounds of the formula (I-2-A-a) may be specificallymentioned: TABLE 13

A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——CH₂—O—(CH₂)₃— —(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃——(CH₂)₂—CHCH₃—(CH₂)₂— —(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂——(CH₂)₂—CH-i-C₃H₇—(CH₂)₂— —(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H_(5—(CH)₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂— —(CH₂)₂—CH—i-OC₃H₇—(CH₂)₂——(CH₂)₂—C(CH₃)₂—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

TABLE 14 A and B are as stated in Table 13 X = 4-Cl—C₆H₄, Z = C₂H₅.

TABLE 15 A and B are as stated in Table 13 X = 4-Cl—C₆H₄, Z = C₃H₇.

TABLE 16 A and B are as stated in Table 13 X = 3,4-Cl₂—C₆H₃, Z = CH₃.

TABLE 17 A and B are as stated in Table 13 X = 3,4-Cl₂—C₆H₃, Z = C₂H₅.

TABLE 18 A and B are as stated in Table 13 X = 3,4-Cl₂—C₆H₃, Z = C₃H₇.

TABLE 19 A and B are as stated in Table 13 X = 4-CF₃—C₆H₄, Z = CH₃.

TABLE 20 A and B are as stated in Table 13 X = 4-CF₃—C₆H₄, Z = C₂H₅.

TABLE 21 A and B are as stated in Table 13 X = 4-CF₃—C₆H₄, Z = C₃H₇.

TABLE 22 A and B are as stated in Table 13 X = 4-Br—C₆H₄, Z = CH₃.

TABLE 23 A and B are as stated in Table 13 X = 4-Br—C₆H₄, Z = C₂H₅.

TABLE 24 A and B are as stated in Table 13 X = 4-Br—C₆H₄, Z = C₃H₇.

Using, for example, according to process (A) ethylN-[1-(5-methyl-3-phenyl)pyrazolylacetyl]-1-aminocyclohexanecarboxylateas starting material, the course of the process according to theinvention can be represented by the following equation:

Using, for example, according to process (B) ethylO-[1-(5-methyl-3-(4-chloro)phenyl)pyrazolylacetyl]-2-hydroxyisobutyrate,the course of the process according to the invention can be representedby the following equation:

Using, for example, according to process (C) ethyl2-[1-(5-methyl-3-phenyl)pyrazolyl]-4-(4-methoxy)benzylmercapto-4-methyl-3-oxovalerate,the course of the process according to the invention can be representedby the following equation:

Using, for example, according to process (Dα)3-[1-(5-methyl-3-(3-chlorophenyl)pyrazolyl]-5,5-dimethylpyrrolidine-2,4-dioneand pivaloyl chloride as starting materials, the course of the processaccording to the invention can be represented by the following equation:

Using, for example, according to process (Dβ)3-[1-(5-ethyl-3-(4-chlorophenyl))pyrazolyl]-4-hydroxy-5-phenyl-Δ³-dihydrofuran-2-oneand acetic anhydride as starting materials, the course of the processaccording to the invention can be represented by the following equation:

Using, for example, according to process (E)3-[1-(5-methyl-3-phenyl)pyrazolyl]-5,5-dimethylpyrrolidine-2,4-dione andethoxyethyl chloroformate as starting materials, the course of theprocess according to the invention can be represented by the followingequation:

Using, for example, according to process (F)3-[1-(5-methyl-3-(4-chlorophenyl))pyrazolyl]-4-hydroxy-5,5-dimethyl-Δ³-dihydrofuran-2-oneand methyl chloromonothiofonnate as starting materials, the course ofthe reaction can be represented as follows:

Using, for example, according to process (G)3-[1-(5-methyl-3-(4-trifluoromethylphenyl))pyrazolyl]-5,5-pentamethylenepyrrolidine-2,4-dioneand methanesulphonyl chloride as starting materials, the course of thereaction can be represented by the following equation:

Using, for example, according to process (H)3-[1-(5-methyl-3-phenyl)pyrazolyl]-4-hydroxy-5,5-dimethyl-Δ³-dihydrofuran-2-oneand 2,2,2-trifluoroethyl methanethiophosphonyl chloride as startingmaterials, the course of the reaction can be represented by thefollowing equation:

Using, for example, according to process (I)3-[1-(5-methyl-3-(4-trifluoromethylphenyl))pyrazolyl]-5-cyclopropyl-5-methylpyrrolidine-24-dioneand NaOH as components, the course of the process according to theinvention can be represented by the following equation:

Using, for example, according to process (Jα)3-[1-(5-methyl-3-(3-trifluoromethylphenyl))pyrazolyl]-4-hydroxy-5-tetramethylene-Δ³-dihydrofuran-2-oneand ethyl isocyanate as starting materials, the course of the reactioncan be represented by the following equation:

Using, for example, according to process (Jβ)3-[1-(5-methyl-3-phenyl)pyrazolyl]-5-methylpyrrolidine-2,4-dione anddimethylcarbamoyl chloride as starting materials, the course of thereaction can be represented by the following scheme:

The compounds, required as starting materials in the process (A)according to the invention, of the formulae (II-A) and (II-B)

in which

A, B, D, X, Y, Z and R⁸ are as defined above

are novel.

The acylamino acid esters of the formulae (II-A) and (II-B) areobtained, for example, when amino acid derivatives of the formula (XV)

in which

A, B, R⁸ and D are as defined above

are acylated with substituted pyrazoylacetic acid derivatives of theformulae (XVI-A) and (XVI-B)

in which

-   -   X, Y and Z are as defined above and    -   W represents a leaving group introduced by reagents for        activating carboxylic acids, such as carbonyldiimidazole,        carbonyldiimides (such as, for example,        dicyclohexylcarbodiimide), phosphorylating agents (such as, for        example, POCl₃, BOP—Cl), halogenating agents, for example        thionyl chloride, oxalyl chloride, phosgene or chloroformic        esters

(Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem. 6,341-5, 1968) or when acylamino acids of the formulae (XVII-A) and(XVII-B)

in which

A, B, D, X, Y and Z are as defined above

are esterified (Chem. Ind. (London) 1568 (1968)).

The compounds of the formulae (XVII-A) and (XVII-B)

in which

A, B, D, X, Y and Z are as defined above

are novel.

The compounds of the formulae (XVII-A) and (XVII-B) are obtained whenamino acids of the formula (XVIII)

in which

A, B and D are as defined above

are acylated with substituted pyrazolylacetic acid derivatives of theformulae (XVI-A) and (XVI-B)

in which

W, X, Y and Z are as defined above,

for example according to Schotten-Baumann (Organikum, VEB DeutscherVerlag der Wissenschaften, Berlin 1977, p. 505).

The compounds of the formula (XVI-A) are novel. Some of the compounds ofthe formula (XVI-B) are novel. They can be prepared by processes knownin principle (EP-A-84822, DE-A-3 203 307, U.S. Pat. No. 4,146,721,DE-A-2 462 459).

The compounds of the formulae (XVI-A) and (XVI-B) are obtained, forexample, by reacting substituted pyrazolylacetic acids of the formulae(XIX-A) and (XIX-B)

in which

X, Y and Z are as defined above

with halogenating agents (for example thionyl chloride, thionyl bromide,oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromideor phosphorus pentachloride), if appropriate in the presence of adiluent (for example optionally chlorinated aliphatic or aromatichydrocarbons, such as toluene or methylene chloride), at temperatures offrom −20° C. to 150° C., preferably from −10° C. to 100° C.

The pyrazolylacetic acids of the formula (XIX-A) are novel. They can beprepared by processes known in principle (Nam, N. L. et al, Chemistry ofHeterocyclic Compounds 34, 382, (1998); L. K. Kulihova, L. V.Cherkesova, Khimiko-Farmatseyticheskii Zhumal, 8, 18-21, (1974)).

Some of the pyrazolylacetic acids of the formula (XIX-B) arecommercially available, some are known, or they can be prepared byprocesses known in principle (U.S. Pat. No. 4,146,721, JP-A-48 028 914,DE-A-1 946 370).

Some of the compounds of the formulae (XV) and (XVIII) are commerciallyavailable and/or known, and/or they can be prepared by known processes(see, for example, Compagnon, Miocque Ann. Chim. (Paris) [14] 5, p.11-22, 23-27 (1970)).

The substituted cyclic aminocarboxylic acids of the formula (XVIIIa) inwhich A and B form a ring are generally obtainable by the Bucherer-Bergssynthesis or by the Strecker synthesis, where they are in each caseobtained in different isomeric forms. Thus, the conditions of theBucherer-Bergs synthesis give predominantly the isomers (for the sake ofsimplicity hereinbelow referred to as β) in which the radicals R and thecarboxyl group are equatorial, whereas the conditions of the Streckersynthesis give predominantly the isomers (for the sake of simplicityhereinbelow referred to as α) in which the amino group and the radicalsR are equatorial.

(L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri, Can.J. Chem. 53, 3339(1975).

Furthermore, the starting materials, used in process (A) above, of theformulae (II-A) and (II-B)

in which

A, B, D, X, Y, Z and R⁸ are as defined above

can be prepared by converting aminonitriles of the formula (XX)

in which

A, B and D are as defined above with substituted pyrazolylacetic acidderivatives of the formulae (XVI-A) and (XVI-B)

in which

W, X, Y and Z are as defined above into compounds of the formulae(XXI-A) and (XXI-B)

in which

A, B, D, X, Y and Z are as defined above and then subjecting these to anacidic alcoholysis.

The compounds of the formulae (XXI-A) and (XXI-B) are likewise novel.

The compounds, required as starting materials for the process (B)according to the invention, of the formulae (III-A) and (III-B)

in which

A, B, X, Y, Z and R⁸ are as defined above

are novel.

They can be prepared by methods known in principle.

Thus, the compounds of the formulae (III-A) and (III-B) are obtained,for example, when 2-hydroxycarboxylic acid esters of the formula (XXII)

in which

A, B and R⁸ are as defined above

are acylated with substituted pyrazolylacetic acid derivatives of theformulae (XVI-A) and (XVI-B)

in which

W, X, Y and Z are as defined above

(Chem. Reviews 52, 237-416 (1953).

Furthermore, compounds of the formulae (III-A) and (III-B) are obtainedwhen substituted pyrazolylacetic acids of the formulae (XIX-A) and(XIX-B)

in which

X, Y and Z are as defined above

are alkylated with α-halocarboxylic acid esters of the formula (XXIII)

in which

A, B and R⁸ are as defined above and

Hal represents chlorine or bromine.

The compounds, required as starting materials for the above process (C),of the formulae (IV-A) and (IV-B)

in which

-   -   A, B, X, Y, Z and R⁸ are as defined above and    -   W¹ represents hydrogen, halogen, alkyl (preferably C₁-C₆-alkyl)        or alkoxy (preferably C₁-C₆-alkoxy)    -   are novel.

They can be prepared by methods known in principle.

The compounds of the formula (IV) are obtained, for example, whensubstituted pyrazolylacetic acid esters of the formulae (XXIV-A) and(XIV-B)

in which

X, Y, Z and R⁸ are as defined above

are acylated with 2-benzylthiocarbonyl halides of the formula (XXV)

in which

A, B and W¹ are as defined above and

Hal represents halogen (in particular chlorine or bromine)

in the presence of strong bases (see, for example, M. S. Chambers, E. J.Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228).

Some of the compounds of the formula (XXIV-A) are novel, and they can beprepared by processes known in principle (EP-A-945 437).

Some of the compounds of the formula (XXIV-B) are commerciallyavailable, some are known, and they can be prepared by processes knownin principle (U.S. Pat. No. 4,146,721, JP-A-48 028 914, DE-A-1 946 370).

The acid halides of the formula (V), carboxylic anhydrides of theformula (VI), chloroformic acid esters or chloroformic acid thioestersof the formula (VII), chloromonothioformic acid esters orchlorodithioformic acid esters of the formula (VIII), sulphonylchlorides of the formula (IX), phosphorus compounds of the formula (X)and metal hydroxides, metal alkoxides or amines of the formula (XI) and(XII), respectively, and isocyanates of the formula (XIII) and carbamoylchlorides of the formula (XIV) furthermore required as startingmaterials for carrying out the processes (D), (E), (F), (G), (H), (I)and (J) according to the invention are generally known compounds oforganic or inorganic chemistry.

Some of the compounds of the formulae (XV), (XVIII), (XX), (XXII),(XXIII) and (XXV) are commercially available, some are known, and/orthey can be prepared by methods known in principle.

Process (A) is characterized in that compounds of the formulae (II-A) or(II-B) in which A, B, D, X, Y, Z and R⁸ are as defined above aresubjected to an intramolecular condensation in the presence of a base.

Suitable diluents for the process (A) according to the invention are allinert organic solvents. Preference is usually given to usinghydrocarbons, such as toluene and xylene, furthermore ethers, such asdibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether anddiglycol dimethyl ether, moreover polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone, andalso alcohols, such as methanol, ethanol, propanol, isopropanol,butanol, isobutanol and tert-butanol.

Suitable bases (deprotonating agents) for carrying out the process (A)according to the invention are all customary proton acceptors.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which may also be used in the presenceof phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464(=methyltri(C₈-C₁₀)alkylammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine). It is furthermore possible to usealkali metals, such as sodium or potassium. Also suitable are alkalimetal and alkaline earth metal amides and hydrides, such as sodiumamide, sodium hydride and calcium hydride, and furthermore also alkalimetal alkoxides, such as sodium methoxide, sodium ethoxide and potassiumtert-butoxide.

When carrying out the process (A) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between −80° C. and180° C., preferably between −50° C. and 120° C.

The process (A) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (A) according to the invention, thereaction components of the formulae (II-A) and (II-B) and thedeprotonating bases are generally employed in approximately twice theequimolar amount. However, it is also possible to use a relatively largeexcess (up to 3 mol) of one or the other component.

The process (B) is characterized in that compounds of the formulae(III-A) and (II-B) in which A, B, X, Y, Z and R⁸ are as defined aboveare subjected to an intramolecular condensation in the presence of adiluent and in the presence of a base.

Suitable diluents for the process (B) according to the invention are allinert organic solvents. Preference is given to using hydrocarbons, suchas toluene and xylene, furthermore ethers, such as dibutyl ether,tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethylether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane,dimethylformamide and N-methylpyrrolidone. It is furthermore possible touse alcohols, such as methanol, ethanol, propanol, isopropanol, butanol,isobutanol and tert-butanol.

Suitable bases (deprotonating agents) for carrying out the process (B)according to the invention are all customary proton acceptors.Preference is given to using alkali metal and alkaline earth metaloxides, hydroxides and carbonates, such as sodium hydroxide, potassiumhydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassiumcarbonate and calcium carbonate, which can also be used in the presenceof phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464(=methyltri(C₈-C₁₀)alkylammonium chloride) or TDA 1(=tris(methoxyethoxyethyl)amine). It is furthermore possible to usealkali metals, such as sodium or potassium. Also suitable are alkalimetal and alkaline earth metal amides and hydrides, such as sodiumamide, sodium hydride and calcium hydride, and furthermore also alkalimetal alkoxides, such as sodium methoxide, sodium ethoxide and potassiumtert-butoxide.

When carrying out the process (B) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between −80° C. and180° C., preferably between −50° C. and 120° C.

The process (B) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (B) according to the invention, thereaction components of the formulae (III-A) and (III-B) and thedeprotonating bases are generally employed in approximately equimolaramounts. However, it is also possible to use a relatively large excess(up to 3 mol) of one or the other component.

The process (C) is characterized in that compounds of the formulae(IV-A) and (IV-B) in which A, B, X, Y, Z and R⁸ are as defined above arecyclized intramolecularly in the presence of an acid and, ifappropriate, in the presence of a diluent.

Suitable diluents for the process (C) according to the invention are allinert organic solvents. Preference is given to using hydrocarbons, suchas toluene and xylene, furthermore halogenated hydrocarbons, such asdichloromethane, chloroform, ethylene chloride, chlorobenzene,dichlorobenzene, moreover polar solvents, such as dimethyl sulphoxide,sulpholane, dimethylformamide and N-methylpyrrolidone. It is furthermorepossible to use alcohols, such as methanol, ethanol, propanol,isopropanol, butanol, isobutanol, tert-butanol.

If appropriate, the acid used can also act as diluent.

Suitable acids for the process (C) according to the invention are allcustomary inorganic and organic acids, such as, for example, hydrohalicacids, sulphuric acid, alkyl-, aryl- and haloalkylsulphonic acids, inparticular halogenated alkylcarboxylic acids, such as, for example,trifluoroacetic acid.

When carrying out the process (C) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between −30° C. and250° C., preferably between 0° C. and 150° C.

The process (C) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (C) according to the invention, thereaction components of the formulae (IV-A) and (IV-B) and the acid areemployed, for example, in equimolar amounts. However, it is alsopossible to use the acid as solvent or as catalyst.

The process (D-α) is characterized in that compounds of the formulae(I-1-A-a) and (I-3-B-a) are in each case reacted with carbonyl halidesof the formula (V), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid binder.

Suitable diluents for the process (D-α) according to the invention areall solvents which are inert to the acid halides. Preference is given tousing hydrocarbons, such as benzine, benzene, toluene, xylene andtetraline, furthermore halogenated hydrocarbons, such as methylenechloride, chloroform, carbon tetrachloride, chlorobenzene ando-dichlorobenzene, moreover ketones, such as acetone and methylisopropyl ketone, furthermore ethers, such as diethyl ether,tetrahydrofuran and dioxane, additionally carboxylic acid esters, suchas ethyl acetate, nitriles, such as acetonitrile, and also stronglypolar solvents, such as dimethylformamide, dimethylacetamide, dimethylsulphoxide and sulpholane. The hydrolytic stability of the acid halidepermitting, the reaction can also be carried out in the presence ofwater.

Suitable acid binders for the reaction according to the process (D-α)according to the invention are all customary acid acceptors. Preferenceis given to using tertiary amines, such as triethylamine, pyridine,diazabicyclooctane (DABCO), diazabicycloundecene (DBU),diazabicyclononene (DBN), Hunig base and N,N-dimethylaniline,furthermore alkaline earth metal oxides, such as magnesium oxide andcalcium oxide, moreover alkali metal and alkaline earth metalcarbonates, such as sodium carbonate, potassium carbonate and calciumcarbonate, and also alkali metal hydroxides, such as sodium hydroxideand potassium hydroxide.

When carrying out the process (D-α) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between −20° C. and+150° C., preferably between 0° C. and 100° C.

When carrying out the processs (D-α) according to the invention, thestarting materials of the formulae (I-1-A-a) and (I-3-B-a) and thecarbonyl halide of the formula (V) are generally each employed inapproximately equivalent amounts. However, it is also possible to use arelatively large excess (up to 5 mol) of the carbonyl halide. Work-up iscarried out by customary methods.

The process (D-β) is characterized in that compounds of the formulae(I-1-A-a) to (I-3-B-a) are reacted with carboxylic acid anhydrides ofthe formula (VI), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid binder.

Suitable diluents for the process (D-β) according to the invention are,preferably, those diluents which are also preferred when acid halidesare used. Furthermore, a carboxylic acid anhydride employed in excessmay simultaneously act as diluent.

Suitable acid binders, which are added, if appropriate, for the process(D-β) are preferably those acid binders which are also preferablyemployed when acid halides are used.

The reaction temperatures in the process (D-β) according to theinvention can be varied within a relatively wide range. In general, theprocess is carried out at temperatures between −20° C. and +150° C.,preferably between 0° C. and 100° C.

When carrying out the process (D-β) according to the invention, thestarting materials of the formulae (I-1-A-a) to (I-3-B-a) and thecarboxylic acid anhydride of the formula (VI) are generally eachemployed in approximately equivalent amounts. However, it is alsopossible to use a relatively large excess (up to 5 mol) of thecarboxylic acid anhydride. Work-up is carried out by customary methods.

In general, diluent and excess carboxylic acid anhydride and thecarboxylic acid that is formed are removed by distillation or by washingwith an organic solvent or with water.

The process (E) is characterized in that compounds of the formulae(I-1-A-a) to (I-3-B-a) are in each case reacted with chloroformic acidesters or chloroformic acid thioesters of the formula (VII), ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid binder.

Suitable acid binders for the reaction according to process (E)according to the invention are all customary acid acceptors. Preferenceis given to using tertiary amines, such as triethylamine, pyridine,DABCO, DBU, DBA, Hünig base and N,N-dimethylaniline, furthermorealkaline earth metal oxides, such as magnesium oxide and calcium oxide,moreover alkali metal and alkaline earth metal carbonates, such assodium carbonate, potassium carbonate and calcium carbonate, and alsoalkali metal hydroxides, such as sodium hydroxide and potassiumhydroxide.

Suitable diluents for the process (E) according to the invention are allsolvents which are inert to the chloroformic acid esters or chloroformicacid thioesters. Preference is given to using hydrocarbons, such asbenzine, benzene, toluene, xylene and tetraline, furthermore halogenatedhydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones,such as acetone and methyl isopropyl ketone, furthermore ethers, such asdiethyl ether, tetrahydrofuran and dioxane, additionally carboxylic acidesters, such as ethyl acetate, nitriles, such as acetonitrile, and alsostrongly polar solvents, such as dimethylformamide, dimethylacetamide,dimethyl sulphoxide and sulpholane.

When carrying out the process (E) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ifthe process is carried out in the presence of a diluent and an acidbinder, the reaction temperatures are generally between −20° C. and+100° C., preferably between 0° C. and 50° C.

The process (E) according to the invention is generally carried outunder atmospheric pressure.

When carrying out the process (E) according to the invention, thestarting materials of the (I-1-A-a) to (I-3-B-a) and the correspondingchloroformic acid ester or chloroformic acid thioester of the formula(VII) are generally each employed in approximately equivalent amounts.However, it is also possible to use a relatively large excess (up to 2mol) of one or the other component. Work-up is carried out by customarymethods. In general, precipitated salts are removed and the reactionmixture that remains is concentrated by removing the diluent underreduced pressure.

The process (F) according to the invention is characterized in thatcompounds of the formulae (I-1-A-a) to (I-3-B-a) are in each casereacted with compounds of the formula (VIII), in the presence of adiluent and if appropriate in the presence of an acid binder.

In the preparation process (F), about 1 mol of chloromonothioformic acidester or chlorodithioformic acid ester of the formula (VIII) is employedper mole of starting material of formulae (I-1-A-a) to (I-3-B-a), atfrom 0 to 120° C., preferably from 20 to 60° C.

Suitable diluents, which are added, if appropriate, are all inert polarorganic solvents, such as nitriles, esters, ethers, amides, sulphones,sulphoxides, but also halogenated alkanes.

Preference is given to using acetonitrile, ethyl acetate, dimethylsulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds(I-1-A-a) to (I-3-B-a) is prepared by addition of strong deprotonatingagents, such as, for example, sodium hydride or potassium tert-butoxide,the further addition of acid binders may be dispensed with.

If acid binders are used, these are suitably customary inorganic ororganic bases, for example sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine, triethylamine.

The reaction can be carried out under atmospheric pressure or underelevated pressure and is preferably carried out under atmosphericpressure. Work-up is carried out by customary methods.

The process (G) is characterized in that compounds of the formulae(I-1-A-a) to (I-3-B-a) are in each case reacted with sulphonyl chloridesof the formula (IX), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid binder.

In preparation process (G), about 1 mol of sulphonyl chloride of theformula (IX) is employed per mole of the starting material of theformulae (I-1-A-a) to (I-3-B-a), at from −20 to 150° C., preferably from20 to 70° C.

Suitable diluents, which are added, if appropriate, are all inert polarorganic solvents, such as nitrites, esters, ethers, amides, sulphones,sulphoxides or halogenated hydrocarbons, such as methylene chloride.

Preference is given to using acetonitrile, ethyl acetate, dimethylsulphoxide, tetrahydrofuran, dimethylformamide, methylene chloride.

If, in a preferred embodiment, the enolate salt of the compounds(I-1-A-a) to (I-3-B-a) is prepared by addition of strong deprotonatingagents (such as, for example, sodium hydride or potassiumtert-butoxide), the further addition of acid binders may be dispensedwith.

If acid binders are used, these are suitably customary inorganic ororganic bases, for example sodium hydroxide, sodium carbonate, potassiumcarbonate, pyridine, triethylamine.

The reaction can be carried out under atmospheric pressure or underelevated pressure and is preferably carried out under atmosphericpressure. Work-up is carried out by customary methods.

The process (H) according to the invention is characterized in thatcompounds of the formulae (I-1-A-a) to (I-3-B-a) are in each casereacted with phosphorus compounds of the formula (X), if appropriate inthe presence of a diluent and if appropriate in the presence of an acidbinder.

In the preparation process (H), 1 to 2, preferably 1 to 1.3, mol of thephosphorus compound of the formula (X) are employed per mole of thecompounds (I-1-A-a) to (I-3-B-a) at temperatures between −40° C. and150° C., preferably between −10 and 110° C., to obtain compounds of theformulae (I-1-A-e) to (I-3-B-e).

Suitable diluents which are added, if appropriate, are all inert polarorganic solvents, such as ethers, amides, nitrites, alcohols, sulphides,sulphones, sulphoxides, etc.

Preference is given to using acetonitrile, dimethyl sulphoxide,tetrahydrofuran, dimethylformamide, methylene chloride.

Suitable acid binders, which are added, if appropriate, are customaryinorganic or organic bases, such as hydroxides, carbonates or amines.Sodium hydroxide, sodium carbonate, potassium carbonate, pyridine andtriethylamine may be mentioned by way of example.

The reaction can be carried out under atmospheric pressure or underelevated pressure and is preferably carried out under atmosphericpressure. Work-up is carried out by customary methods of organicchemistry. Purification of the resulting end products is preferablycarried out by crystallization, chromatographic purification or by“incipient distillation”, i.e. removal of the volatile components underreduced pressure.

The process (I) is characterized in that compounds of the formulae(I-1-A-a) to (I-3-B-a) are reacted with metal hydroxides or metalalkoxides of the formula (XI) or amines of the formula (XII), ifappropriate in the presence of a diluent.

Preferred diluents for the process (I) according to the invention areethers, such as tetrahydrofuran, dioxane, diethyl ether, or elsealcohols, such as methanol, ethanol, isopropanol, and also water.

The process (I) according to the invention is generally carried outunder atmospheric pressure.

The reaction temperatures are generally between −20° C. and 1 00° C.,preferably between 0° C. and 50° C.

The process (J) according to the invention is characterized in thatcompounds of the formulae (I-1-A-a) to (I-3-B-a) are in each casereacted with compounds of the formula (XIII) (J-α), if appropriate inthe presence of a diluent and if appropriate in the presence of acatalyst, or (J-β) with compounds of the formula (XIV), if appropriatein the presence of a diluent and if appropriate in the presence of anacid binder.

In preparation process (J-α), about 1 mol of isocyanate of the formula(XIII) is employed per mole of the starting material of the formulae(I-1-A-a) to (I-3-B-a), at from 0 to 100° C., preferably at from 20 to50° C.

Suitable diluents, which are added, if appropriate, are all inertorganic solvents, such as ethers, amides, nitrites, sulphones,sulphoxides.

If appropriate, catalysts may be added to accelerate the reaction.Particularly advantageous for use as catalysts are organotin compounds,such as, for example, dibutyltin dilaurate. The process is preferablycarried out at atmospheric pressure.

In the preparation process (J-β), about 1 mol of carbamoyl chloride ofthe formula (XIV) is employed per mole of starting material of theformulae (I-1-A-a) to (I-3-B-a), at from −20 to 150° C., preferably atfrom 0 to 70° C.

Suitable diluents, which are added, if appropriate, are all inert polarorganic solvents, such as nitrites, esters, ethers, amides, sulphones,sulphoxides or halogenated hydrocarbons.

The active compounds are suitable for protecting plants and plantorgans, for increasing the harvest yield, for improving the quality ofthe harvested goods and for controlling animal pests, in particularinsects, arachnids and nematodes, which are encountered in agriculture,in forestry, in gardens and leisure facilities, in the protection ofstored products and of materials, and in the hygiene sector, and havegood plant tolerance, favourable toxicity to warm-blooded animals andgood environmental compatibility. They may preferably be employed ascrop protection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Annadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. andSchistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp. andDamalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi and Frankliniella accidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneuraflumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Antrionomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp. and Brevipalpus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides ormicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they can also be employed as intermediates or precursorsfor the synthesis of other active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, including the transgenicplants and inclusive of the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodas meaning all parts and organs of plants above and below the ground,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on the surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on, injecting and, in thecase of propagation material, in particular in the case of seeds, alsoby applying one or more coats.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics or chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

As solid carriers there are suitable:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly disperse silica,alumina and silicates; as solid carriers for granules there aresuitable: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, and also syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks;as emulsifiers and/or foam-formers there are suitable: for examplenonionic and anionic emulsifiers, such as polyoxyethylene fatty acidesters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonatesand also protein hydrolysates; as dispersants there are suitable: forexample lignosulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be employed as suchor in their formulations as a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides in order toincrease the activity spectrum or avoid the development of resistance.In many cases synergistic effects are achieved, i.e. the efficacy of themixture is greater than the efficacy of the individual components.

Suitable co-components in mixtures are, for example, the followingcompounds:

Fungicides:

aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimate, buthiobate,

calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

farnoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimzone, fluazinamn, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,furconazole-cis, furmecyclox,

guazatine,

hexachlorobenzene, hexaconazole, hyrnexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulfocarb, methfuiroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,picoxystrobin, pimaricin, piperalin, polyoxin, polyoxorim, probenazole,prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole,propineb, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil,pyroquilon, pyroxyfur,

quinconazole, quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,trifloxystrobin, triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801,

α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,

α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)phenyl]methylene]-1H-1,2,4-triazole-1-ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

(E)-α-(methoxyimino)-N-methyl-2-phenoxyphenylacetamide,

1-isopropyl{2-methyl-1-[[[1-(4-methylphenyl)ethyl]amino]carbonyl]propyl}carbamate,

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone-O-(phenylmethyl)oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,

1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,

1-[(diiodomethyl)sulphonyl]-4-methylbenzene,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]methyl]-1H-1,2,4-triazole,

1-[1-[2-[(2,4-dichlorophenyl)methoxy]phenyl]ethenyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,

2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N-[1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclopropanecarboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinylthiocyanate,

2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)phenyl]methyl]benzamide,

2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(1-methylethyl)sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2-(bromomethyl)pentanedinitrile,

2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)acetamide,

2-phenylphenol (OPP),

3,4-dichloro-1-[4-(difluoromethoxy)phenyl]-1H-pyrrole-2,5-dione,

3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)oxy]methyl]benzamide,

3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

4-methyltetrazolo[1,5-a]quinazolin-5(4H)-one,

8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,

8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)carbonyl]-9-carboxylic hydrazide,

bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)oxy]-2,5-thiophenedicarboxylate,

cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol,

cis-4-[3-[4-(1,1-dimethylpropyl)phenyl-2-methylpropyl]-2,6-dimethylmorpholinehydrochloride,

ethyl[(4-chlorophenyl)azo]cyanoacetate,

potassium bicarbonate,

methanetetrathiol-sodium salt,

methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)acetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitrobenzenesulphonamide,

N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)acetamide,

N-(6-methoxy)-3-pyridinylcyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)amino]ethyl]benzamide,

N-[3-chloro-4,5-bis(2-propinyloxy)phenyl]-N′-methoxymethanimidamide,

N-formyl-N-hydroxy-DL-alanine-sodium salt,

O,O-diethyl[2-(dipropylamino)-2-oxoethyl]ethylphosphoramidothioate,

O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran]-3′-one,

4-[3,4-dimethoxyphenyl)-3-(4-fluorophenyl)acryloyl]morpholine

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, acephate, acetarniprid, acequinocyl, acrinathrin, alanycarb,aldicarb, aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz,avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphosM, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillusthuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella,bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,bifenazate, bifenthrin, bioethanomethrin, biopermethrin, bistrifluron,BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim,butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,chlovaporthrin, chromafenozide, cis-resmethrin, cispermethrin,clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos,cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine,

deltanethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlorvos, dicofol, diflubenzuron, dimethoate,dimethylvinphos, dinetofuran, diofenolan, disulfoton, docusat-sodium,dofenapyn,

eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,esfenvalerate, ethiofencarb, ethion, ethiprole, ethoprophos, etofenprox,etoxazole, etrimfos, fenarniphos, fenazaquin, fenbutatin oxide,fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin,fenpyrad, fenpyrithrin, fenpyroximate, fenthian, fenvalerate, fipronil,fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,flufenoxuron, flumethrin, flupyrazofos, flutenzine, fluvalinate,fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb,

granulosis viruses,

halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,

imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,

nuclear polyhedrosis viruses,

lambda-cyhalothrin, lufenuron,

malathion, mecarbam, metaldehyde, methamidophos, Metharhiziumanisopliae, Metharhizium flavoviride, methidathion, methiocarb,methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone,mevinphos, milbemectin, milbemycin, monocrotophos,

naled, nitenpyram, nithiazine, novaluron,

omethoate, oxamyl, oxydemethon M,

Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,propargite, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos,pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,pyriproxyfen,

quinalphos,

ribavirin,

salithion, sebufos, silafluofen, spinosad, spirodiclofen, sulfotep,sulprofos,

tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,tetrachlorvinphos, tetradifon, theta-cypermethrin, thiacloprid,thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate,thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin,triarathene, triazamate, triazophos, triazuron, trichlophenidine,trichlorfon, triflumuron, trimethacarb,

vamidothion, vaniliprole, Verticillium lecanii,

YI 5302,

zeta-cypermethrin, zolaprofos,

(1R-cis)-[5-(phenylmethyl)-3-furanyl]methyl3-[(dihydro-2-oxo-3(2H)-furanylidene)methyl]-2,2-dimethylcyclopropanecarboxylate,

(3-phenoxyphenyl)methyl 2,2,3,3-tetramethylcyclopropanecarboxylate,

1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,

2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydrooxazole,

2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,

2-chloro-N-[[[4-(1-phenylethoxy)phenyl]amino]carbonyl]benzamide,

2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)phenyl]amino]carbonyl]benzamide,

3-methylphenyl propylcarbamate,

4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxybenzene,

4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,

4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,

4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,

Bacillus thuringiensis strain EG-2348,

[2-benzoyl-1-(1,1-dimethylethyl)hydrazinobenzoic acid,

2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-ylbutanoate,

[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]cyanamide,

dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,

ethyl[2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]carbamate,

N-(3,4,4-trifluoro-1-oxo-3-butenyl)glycine,

N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,

N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitroguanidine,

N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,

N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,

O,O-diethyl-[2-(dipropylamino)-2-oxoethyl]ethylphosphoramidothioate,

N-cyanomethyl-4-trifluoromethylnicotinamide,

3,5-dichloro-1-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)propoxy]benzene.

It is also possible to admix other known active compounds, such asherbicides, or fertilizers and growth regulators, safeners andsemiochemicals.

When used as insecticides, the active compounds according to theinvention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents. Synergistic agents are compoundswhich increase the action of the active compounds, without it beingnecessary for the synergistic agent added to be active itself.

When used as insecticides, the active compounds according to theinvention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with inhibitors which reduce the degradation of the activecompound after use in the vicinity of the plant, on the surface of partsof plants or in plant tissue.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as by a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are understood as meaning plants with novelproperties (“traits”) which are grown by conventional cultivation, bymutagenesis or by recombinant DNA techniques. These may be cultivars,biotypes or genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferably to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparted particularly advantageoususeful properties (“traits”) to these plants. Examples of suchproperties are better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products. Further andparticularly emphasized examples of such properties are a better defenseof the plants against animal and microbial pests, such as againstinsects, mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, tobacco, oilseed rape and also fruit plants (with thefruits apples, pears, citrus fruits and grapes), and particular emphasisis given to maize, soya beans, potatoes, cotton, tobacco and oilseedrape. Traits that are emphasized are in particular increased defense ofthe plants against insects, arachnids, nematodes and slugs and snails bytoxins formed in the plants, in particular those formed in the plants bythe genetic material from Bacillus thuringiensis (for example by thegenes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9cCry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelowreferred to as “Bt plants”). Traits which are also particularlyemphasized are the increased resistance of plants to fungi, bacteria andviruses by systemic acquired resistance (SAR), systemin, phytoalexins,elicitors and resistance genes and the correspondingly expressedproteins and toxins. Traits that are furthermore particularly emphasizedare the increased tolerance of the plants to certain herbicidally activecompounds, for example imidazolinones, sulphonylureas, glyphosate orphosphinotricin (for example the “PAT” gene). The genes which impart thedesired traits in question can also be present in combination with oneanother in the transgenic plants. Examples of “Bt plants” which may bementioned are maize varieties, cotton varieties, soya bean varieties andpotato varieties which are sold under the trade names YIELD GARD® (forexample maize, cotton, soya beans), KnockOut® (for example maize),StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) andNewLeaf® (potato). Examples of herbicide-tolerant plants which may bementioned are maize varieties, cotton varieties and soya bean varietieswhich are sold under the trade names Roundup Ready® (tolerance toglyphosate, for example maize, cotton, soya bean), Liberty Link®(tolerance to phosphinotricin, for example oilseed rape), IMI®(tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, forexample maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize). Of course, these statements also apply to plant cultivars havingthese genetic traits or genetic traits still to be developed, whichcultivars will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the formula I orthe active compound mixtures according to the invention. The preferredranges stated above for the active compounds or mixtures also apply tothe treatment of these plants. Particular emphasis is given to thetreatment of plants with the compounds or mixtures specificallymentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, harvest mites, flies (biting andlicking), parasitic fly larvae, lice, hair lice, feather lice and fleas.These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example Blatta orientalis,Periplaneta americana, Blattella germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Stemostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) und Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injection(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) can be used as formulations (for example powders,emulsions, free-flowing compositions), which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as preferred -but without limitation:

Beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobiusmollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctusplanicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale,Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apatemonachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylonspec., and Dinoderus minutus.

Hymenopterons, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerusaugur.

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentsaccording to the invention or mixtures comprising these are to beunderstood as meaning, for example:

building timber, wooden beams, railway sleepers, bridge components, boatjetties, wooden vehicles, boxes, pallets, containers, telegraph poles,wood panelling, wooden windows and doors, plywood, chipboard, joinery orwooden products which are used quite generally in house-building or inbuilding joinery.

The active compounds can be used as such, in the form of concentrates orgenerally customary formulations, such as powders, granules, solutions,suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent, awater repellent, if appropriate siccatives and UV stabilizers and ifappropriate dyestuffs and pigments, and also other processingauxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by series oftests. In general, however, it is sufficient to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., terpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablycc-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, providing that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture or an aliphatic polar organic chemicalsolvent or solvent mixture is replaced. Aliphatic organic chemicalsolvents containing hydroxyl and/or ester and/or ether groups, such as,for example, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-coumaroneresin, silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or one drying vegetable oil.Alkyd resins having an oil content of more than 45% by weight,preferably 50 to 68% by weight, are preferably used according to theinvention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid,methoxyphenoxide, triflumuron, chlothianidine, spinosad and tefluthrin,

and also fungicides, such as epoxyconazole, hexaconazole, azaconazole,propiconazole, tebuconazole, cyproconazole, metconazole, imazalil,dichlorfluanid, tolylfluanid, 3-iodo-2-propinylbutyl carbamate,N-octylisothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with saltwateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., in particular fouling by sessile Entomostraka groups, which comeunder the generic term Cirripedia (cirriped crustaceans), is ofparticular importance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)bismuth chloride, tri-n-butyltin fluoride, manganeseethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylenebisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, flugicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

algicides such as

2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,dichlorophen, diuron, endothal, fentin acetate, isoproturon,methabenzthiazuron, oxyfluorfen, quinoclaamine and terbutryn;

fungicides such as

benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,tolylfluanid and azoles such as azaconazole, cyproconazole,epoxyconazole, hexaconazole, metconazole, propiconazole andtebuconazole;

molluscicides such as

fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb andtrimethacarb, Fe-chelates;

or conventional antifouling active compounds such as

4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium,copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,pyridinetriphenylborane, tetrabutyldistannoxane,2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine,2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide and2,4,6-trichlorophenylmaleiimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/-acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, inparticular insects, arachnids and mites, which are found in enclosedspaces such as, for example, dwellings, factory halls, offices, vehiclecabins and the like. They can be employed alone or in combination withother active compounds and auxiliaries in domestic insecticide productsfor controlling these pests. They are active against sensitive andresistant species and against all developmental stages. These pestsinclude:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus andDermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae and Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium and Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus andPorcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus andPolydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina and Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa and Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp. andReticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp. andLiposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais and Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,Stomoxys calcitrans and Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella and Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans and Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp. and Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis and Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus and Triatoma infestans.

In the field of household insecticides, they are used alone or incombination with other suitable active compounds, such as phosphoricacid esters, carbamates, pyrethroids, neonicotinoides, growth regulatorsor active compounds from other known classes of insecticides.

They are used as aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free or passive evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

The active compounds according to the invention can also be used asdefoliants, desiccants, haulm killers and, especially, as weedkillers.Weeds in the broadest sense are understood to mean all plants which growin locations where they are undesired. Whether the substances accordingto the invention act as total or selective herbicides dependsessentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia,Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus,Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium,Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus,Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha,Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum,Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola,Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea,Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola,Xanthium.

Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis,Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca,Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis,Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina,Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis,Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera,Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum,Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria,Sorghum.

Monocotyledonous crops of the genera: Allium, Ananas, Asparagus, Avena,Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale,Triticum, Zea.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The active compounds according to the invention are suitable, dependingon the concentration, for the total control of weeds, for example onindustrial terrain and rail tracks, and on paths and areas with andwithout tree plantings. Similarly, the active compounds according to theinvention can be employed for controlling weeds in perennial crops, forexample forests, decorative tree plantings, orchards, vineyards, citrusgroves, nut orchards, banana plantations, coffee plantations, teaplantations, rubber plantations, oil palm plantations, cocoaplantations, soft fruit plantings and hop fields, on lawns, turf andpastureland, and for the selective control of weeds in annual crops.

The compounds of the formula (I) according to the invention have strongherbicidal activity and a broad active spectrum when used on the soiland on above-ground parts of plants. To a certain extent they are alsosuitable for the selective control of monocotyledonous anddicotyledonous weeds in monocotyledonous and dicotyledonous crops, bothby the pre-emergence and by the post-emergence method.

At certain concentrations or application rates, the active compoundsaccording to the invention can also be employed for controlling animalpests and fuigal or bacterial plant diseases. If appropriate, they canalso be used as intermediates or precursors for the synthesis of otheractive compounds.

The active compounds can be converted into the customary formulationssuch as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric materials.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents and/orsolid carriers, optionally with the use of surfactants, that is,emulsifiers and/or dispersants, and/or foam formers.

If the extender used is water, it is also possible to employ, forexample, organic solvents as auxiliary solvents. Essentially, suitableliquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water.

Suitable solid carriers are: for example ammonium salts and groundnatural minerals such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals such as finely divided silica, alumina and silicates; suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,or else synthetic granules of inorganic and organic meals, and granulesof organic material such as sawdust, coconut shells, maize cobs andtobacco stalks; suitable emulsifiers and/or foam formers are: forexample nonionic and anionic emulsifiers such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates,or else protein hydrolysates; suitable dispersants are: for examplelignosulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention,as such or in their formulations, can also be used as mixtures withknown herbicides and/or substances which improve the compatibility withcrop plants (“safeners”), finished formulations or tank mixes beingpossible. Also possible are mixtures with weed-killers comprising one ormore known herbicides and a safener.

Possible components for the mixtures are known herbicides, for example

acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos,asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin(-ethyl), benfuresate, bensulfuron (-methyl), bentazon, benzfendizone,benzobicyclon, benzofenap, benzoylprop (-ethyl), bialaphos, bifenox,bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor,butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim,carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben,chloridazon, chlorimuron (-ethyl), chlomitrofen, chlorsulfuron,chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim,clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid,clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine,cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl),2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (-P),diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat,diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor,dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid,diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb,ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen,ethoxysulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide,flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam,fluazifop (-P-butyl), fluazolate, flucarbazone (-sodium), flufenacet,flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn,flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl),flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr (-butoxypropyl, -meptyl), flurprimidol,flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron,glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen,haloxyfop (-ethoxyethyl, -P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin,imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil,isopropalin, isoproturon, isouron, isoxaben, isoxachlortole,isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, mecoprop,mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron,metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron,metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide,napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin,oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen,paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone,phemnedipham, picolinafen, piperophos, pretilachlor, primisulfuron(-methyl), profluazol, prometryn, propachlor, propanil, propaquizafop,propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb,prosulfuron, pyraflufen (-ethyl), pyrazogyl, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol,pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac,quinmerac, quinoclamine, quizalofop (-P-ethyl, -P-tefuryl), rimsulfuron,sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim,terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr,thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil,tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr,tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl),tritosulfuron.

Furthermore suitable for the mixtures are known safeners, for example:

AD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil, 2,4-D,DKA-24, dichlormid, dymron, fenclorim, fenchlorazol (-ethyl), flurazole,fluxofenim, furilazole, isoxadifen (-ethyl), MCPA, mecoprop (-P),mefenpyr (-diethyl), MG-191, oxabetrinil, PPG-1292, R-29148.

A mixture with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in a customary manner, for example bywatering, spraying, atomizing or broadcasting.

The active compounds according to the invention can be applied bothbefore and after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a relatively widerange. It depends essentially on the nature of the desired effect. Ingeneral, the amounts used are between 1 g and 10 kg of active compoundper hectare of soil surface, preferably between 5 g and 5 kg per ha.

The substances according to the invention have potent microbicidalactivity and can be employed for controlling undesirable microorganisms,such as fungi and bacteria, in crop protection and in the protection ofmaterials.

Fungicides can be employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come underthe generic names listed above may be mentioned as examples, but not byway of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea

(conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Altemaria species, such as, for example, Altemaria brassicae; and

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The active compounds according to the invention also have very goodfortifying action in plants. Accordingly, they can be used formobilizing the defences of the plant against attack by undesirablemicroorganisms.

In the present context, plant-fortifying (resistance-inducing)substances are to be understood as meaning those substances which arecapable of stimulating the defense system of plants such that, when thetreated plants are subsequently inoculated with undesirablemicroorganisms, they show substantial resistance to thesemircroorganisms.

In the present case, undesirable microorganisms are to be understood asmeaning phytopathogenic fungi, bacteria and viruses. Accordingly, thesubstances according to the invention can be used to protect plants fora certain period after the treatment against attack by the pathogensmentioned. The period for which protection is provided generally extendsover 1 to 10 days, preferably 1 to 7 days, after the treatment of theplants with the active compounds.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

The active compounds according to the invention are also suitable forincreasing the yield of crops. In addition, they show reduced toxicityand are well tolerated by plants.

At certain concentrations and application rates, the active compoundsaccording to the invention can also be used as herbicides, forinfluencing plant growth and for controlling animal pests. Ifappropriate, they can also be used as intermediates and precursors forthe synthesis of further active compounds.

In the protection of materials, the compounds according to the inventioncan be employed for protecting industrial materials against infectionwith, and destruction by, undesired microorganisms.

Industrial materials in the present context are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with, or destroyed by, microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the proliferation of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably adhesives, sizes, paper and board, leather,wood, paints, cooling lubricants and heat-transfer liquids, particularlypreferably wood.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular moulds, wood-discolouringand wood-destroying fungi (Basidiomycetes), and against slime organismsand algae.

Microorganisms of the following genera may be mentioned as examples:Altemaria, such as Altemaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, and

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted into the customary formulations, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsulations in polymeric substances and in coatingcompositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants, and/or foamformers. If the extender used is water, it is also possible to employ,for example, organic solvents as auxiliary solvents.

Essentially, suitable liquid solvents are: aromatics such as xylene,toluene or alkylnaphthalenes, chlorinated aromatics or chlorinatedaliphatic hydrocarbons such as chlorobenzenes, chloroethylenes ormethylene chloride, aliphatic hydrocarbons such as cyclohexane orparaffins, for example petroleum fractions, alcohols such as butanol orglycol and their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, or elsewater. Liquefied gaseous extenders or carriers are to be understood asmeaning liquids which are gaseous at standard temperature and underatmospheric pressure, for example aerosol propellants such ashalogenated hydrocarbons, or else butane, propane, nitrogen and carbondioxide. Suitable solid carriers are: for example ground naturalminerals such as kaolins, clays, talc, chalk, quartz, attapulgite,montmorillonite or diatomaceous earth, and ground synthetic mineralssuch as finely divided silica, alumina and silicates. Suitable solidcarriers for granules are: for example crushed and fractionated naturalrocks such as calcite, marble, pumice, sepiolite and dolomite, or elsesynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks. Suitable emulsifiers and/or foam formers are: for examplenonionic and anionic emulsifiers, such as polyoxyethylene fatty acidesters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates,or else protein hydrolysates. Suitable dispersants are: for examplelignosulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such orin their formulations, also in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, to broaden, forexample, the activity spectrum or to prevent development of resistance.In many cases, synergistic effects are obtained, i.e. the activity ofthe mixture is greater than the activity of the individual components.

Examples of suitable mixing components are the following:

Fungicides:

2-phenylphenol; 8-hydroxyquinolin sulphate; acibenzolar-S-methyl;aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim;anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; benomyl;benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos;binapacryl; biphenyl; bitertanol; blasticidin-S; bromuconazole;bupirimate; buthiobate; butylamine; calcium polysulphide; capsimycin;captafol; captan; carbendazim; carboxin; carpropamid; carvone;quinomethionate; chlobenthiazone; chlorfenazole; chloroneb;chlorothalonil; chlozolinate; clozylacon; cyazofamid; cyflufenamid;cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb;dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine;dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol;dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap;diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon;edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram;fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin;fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover;flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol;flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-Al;fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil;fulrmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazole;imazalil; imibenconazole; iminoctadine triacetate; iminoctadinetris(albesil); iodocarb; ipconazole; iprobenfos; iprodione;iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin;kresoxim-methyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil;metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam;metiram; metominostrobin; metsulfovax; mildiomycin; myclobutanil;myclozolin; natamycin; nicobifen; nitrothal-isopropyl; noviflumuron;nuarimol; oflirace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole;oxycarboxin; oxyfenthiin; paclobutrazole; pefurazoate; penconazole;pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins;polyoxorim; probenazole; prochloraz; procymidone; propamocarb;propanosine-sodium; propiconazole; propineb; proquinazid;prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil;pyroquilon; pyroxyfur; pyrrolenitrine; quinconazole; quinoxyfen;quintozene; simeconazole; spiroxamine; sulphur; tebuconazole;tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole;thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid;tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil;triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin;triflumizole; triforine; triticonazole; uniconazole; validamycin A;vinclozolin; zineb; ziram; zoxamide;(2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methyl-sulphonyl)amino]butanamide;1-(1-naphthalenyl)-1H-pyrrole-2,5-dione;2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine;2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide;2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide;3,4,5-trichloro-2,6-pyridinedicarbonitrile; actinovate;cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol; methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate;monopotassium carbonate;N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide;N-butyl-8-(1,1-dimethylethyl)-1-oxaspiro[4.5]decane-3-amine; sodiumtetrathiocarbonate;

and copper salts and preparations, such as Bordeaux mixture; copperhydroxide; copper naphthenate; copper oxychloride; copper sulphate;cufraneb; copper oxide; mancopper; oxine-copper.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole,acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb,aldoxycarb, allethrin, allethrin 1R-isomers, alpha-cypermethrin(alphamethrin), amidoflumet, aminocarb, amitraz, avermectin, AZ-60541,azadirachtin, azamethiphos, azinphos-methyl, azinphos-ethyl,azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillusthuringiensis, Bacillus thuringiensis strain EG-2348, Bacillusthuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821,baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb,benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin,bifenazate, bifenthrin, binapacryl, bioallethrin,bioallethrin-S-cyclopentyl-isomer, bioethanomethrin, biopermethrin,bioresmethrin, bistrifluron, BPMC, brofenprox, bromophos-ethyl,bromopropylate, bromfenvinfos (-methyl), BTG-504, BTG-505, bufencarb,buprofezin, butathiofos, butocarboxim, butoxycarboxim, butylpyridaben,

cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion,carbosulfan, cartap, CGA-50439, quinomethionate, chlordane,chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr,chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate,chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl),chlovaporthrin, chromafenozide, cis-cypermethrin, cis-resmethrin,cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin,clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene,cycloprothrin, Cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyphenothrin (IR-trans-isomer), cyromazine,

DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphone,diafenthiuron, dialifos, diazinon, dichlofenthion, dichlorvos, dicofol,dicrotophos, dicyclanil, diflubenzuron, dimethoate, dimethylvinphos,dinobuton, dinocap, dinotefuran, diofenolan, disulfoton, docusat-sodium,dofenapyn, DOWCO-439,

eflusilanate, emamectin, emamectin-benzoate, empenthrin (1R-isomer),endosulfan, Entomopthora spp., EPN, esfenvalerate, ethiofencarb,ethiprole, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,

famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin,fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb,fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fensulfothion,fenthion, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim,fluazuron, flubenzimine, fluorocythrinate, flucycloxuron, flucythrinate,flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrazofos,flutenzin (flufenzine), fluvalinate, fonofos, formetanate, formothion,fosmethilan, fosthiazate, fubfenprox (fluproxyfen), furathiocarb,

gamma-HCH, gossyplure, grandlure, granulosis viruses,

halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron,hexythiazox, hydramethylnone, hydroprene,

IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenphos,iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin,

japonilure,

kadethrin, nuclear polyhedrosis viruses, kinoprene,

lambda-cyhalothrin, lindane, lufenuron,

malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium,methacrifos, methamidophos, Metharhizium anisopliae, Metharhiziumflavoviride, methidathion, methiocarb, methomyl, methoprene,methoxychlor, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,milbemectin, milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin,MTI-800,

naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine,nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768,novaluron, noviflumuron,

OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl,oxydemeton-methyl,

Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl),permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (IR-transisomer), phenthoate, phorate, phosalone, phosmet, phospharnidon,phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphos-methyl,pirimiphos-ethyl, prallethrin, profenofos, promecarb, propaphos,propargite, propetamphos, propoxur, prothiofos, prothoate,protrifenbute, pymetrozine, pyraclofos, pyresmethrin, pyrethrum,pyridaben, pyridalyl, pyridaphenthion, pyridathion, pyrimidifen,pyriproxyfen,

quinalphos,

resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,

S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad,spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos, SZI-121,

tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos,teflubenzuron, tefluthrin, temephos, temivinphos, terbam, terbufos,tetrachlorvinphos, tetradifon, tetramethrin, tetramethrin (1R-isomer),tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam, thiapronil,thiatriphos, thiocyclam hydrogenoxalate, thiodicarb, thiofanox,thiometon, thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin,tralomethrin, transfluthrin, triarathene, triazamate, triazophos,triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,

vamidothion, vaniliprole, verbutin, Verticillium lecanii,

WL-108477, WL-40027,

YI-5201, YI-5301, YI-5302,

XMC, xylylcarb,

ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901,

the compound 3-methylphenyl propylcarbamate (tsumacide Z),

the compound3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]-octane-3-carbonitrile(CAS-Reg. No. 185982-80-3) and the corresponding 3-endo-isomer (CAS-Reg.No. 185984-60-5) (cf. WO-96/37494, WO-98/25923),

and preparations which comprise insecticidally active plant extracts,nematodes, fungi or viruses.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, is also possible.

In addition, the compounds of the formula (I) according to the inventionalso have very good antimycotic activity. They have a very broadantimycotic activity spectrum in particular against dermatophytes andyeasts, moulds and diphasic fungi (for example against Candida species,such as Candida albicans, Candida glabrata), and Epidermophytonfloccosum, Aspergillus species, such as Aspergillus niger andAspergillus fumigatus, Trichophyton species, such as Trichophytonmentagrophytes, Microsporon species such as Microsporon canis andaudouinii. The list of these fungi by no means limits the mycoticspectrum covered, but is only for illustration.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. Application is carried out in a customary manner, forexample by watering, spraying, atomizing, broadcasting, dusting,foaming, spreading, etc. It is furthermore possible to apply the activecompounds by the ultra-low-volume method, or to inject the activecompound preparation or the active compound itself into the soil. It isalso possible to treat the seeds of the plants.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the kind of application. For the treatment of partsof plants, the active compound application rates are generally between0.1 and 10 000 g/ha, preferably between 10 and 1000 g/ha. For seeddressing, the active compound application rates are generally between0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 gper kilogram of seed. For the treatment of the soil, the active compoundapplication rates are generally between 0.1 and 10 000 g/ha, preferablybetween 1 and 5000 g/ha.

The preparation and the use of the active compounds according to theinvention is illustrated by the examples below.

PREPARATION EXAMPLES Example No. I-1-A-a-1

At 20° C., 5.28 g of the compound of Example II-A-1 in 11 ml ofanhydrous DMF (dimethylformamide) are added dropwise to 3.54 g (0.029mol) of potassium tert-butoxide in 17 ml of anhydrous DMF, and themixture is stirred at 40° C. for 1 h.

The reaction solution is stirred into 150 ml of ice-water and acidifiedwith concentrated hydrochloric acid, and the solvent is evaporated. Theresidue is boiled twice with 50 ml of methanol, and the methanol isconcentrated under reduced pressure. The resulting residue is once moreheated in 20 ml of methanol and allowed to cool, and the precipitate isfiltered off with suction.

Yield: 2.55 g (52% of theory), m.p. 256° C.

Analogously to Example (I-1-A-a-1) and in accordance with the generalstatements about the preparation, the following compounds of theformulae (I-1-A-a) and (I-1-B-a) are obtained: (I-1-A-a)

(I-1-B-a) Iso- Ex. No. X Y Z D A B m. p. ° C. mer I-1-A-a-2 3-Cl—C₆H₄ HCH₃ H CH₃ CH₃ 260 — I-1-A-a-3 3-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂—270 β I-1-A-a-4 4-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— >300 βI-1-A-a-5 C₆H₅ H CH₃ H CH₃ CH₃ 263 — I-1-A-a-6 4-Cl—C₆H₄ H CH₃ H—(CH₂)₂—O—(CH₂)₂— 371 — I-1-A-a-7 4-Cl—C₆H₄ H C₂H₅ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 245 β I-1-A-a-8 4-Cl—C₆H₄ H C₃H₇ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 375 β I-1-A-a-9 3-CF₃—C₆H₄ H CH₃ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 275 β I-1-A-a-10 3,4-Cl_(2—C) ₆H₃ H CH₃ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 353 β I-1-A-a-11 3-Br—C₆H₄ H CH₃ H—(CH₂)₂—CHOCH₃—(CH₂)₂— 259 β I-1-A-a-12 4-Cl—C₆H₄ H CH₃

H H 228 — I-1-A-a-13 4-Cl—C₆H₄ H CH₃ —(CH₂)₄— H 164 — I-1-A-a-144-Br-C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— 241 β I-1-A-a-15 4-Cl—C₆H₄ HC₃H₇ H CH₃ CH₃ 176 d — I-1-A-a-16 4-Cl—C₆H₄ H C₂H₅ H CH₃ CH₃ 260 d —I-1-A-a-17 4-Br—C₆H₄ H CH₃ H CH₃ CH₃ 260 d — I-1-A-a-18 4-Cl—C₆H₄ H CH₃H —CH₂—O—(CH₂)₃— 250 — I-1-A-a-19 3,4-Cl₂—C₆H₃ H CH₃ H CH₃ CH₃ 254 —I-1-A-a-20 3-CF₃—C₆H₄ H CH₃ H CH₃ CH₃ 228 — I-1-A-a-21 3-Br—C₃H₄ H CH₃ HCH₃ CH₃ 248 — I-1-B-a-1 4-Cl—C₆H₄ CH₃ CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— 315 βI-1-B-a-2 4-Cl—C₆H₄ CH₃ CH₃ H CH₃ CH₃ 279 — I-1-B-a-3 3-CF₃—C₆H₄ CH₃ CH₃H —(CH₂)₂—CHOCH₃—(CH₂)₂— 245 βd = point of decomposition

Example No. I-1-A-b-1

Under reflux, 0.23 g of isobutyryl chloride and 2 ml of anhydrous ethylacetate are added to 0.78 g of the compound of Preparation ExampleI-1-A-a-4 in 30 ml of anhydrous ethyl acetate and 0.3 ml oftriethylamine. After the reaction has ended (monitored by thin-layerchromatograpy), the solvent is distilled off, the residue is taken up in50 ml of dichloromethane, washed twice with in each case 10 ml of 0.5 NNaOH solution and dried and the solvent is distilled off. The residue ispurified by silica gel column chromatography (methylene chloride:ethylacetate, 3:1).

Yield: 0.65 g (71% of theory), m.p. 226° C.

Analogously to Example (I-1-A-b-1) and in accordance with the generalstatements about the preparation, the following compounds of theformulae (I-1-A-b) and (I-1-B-b) (I-1-A-b)

(I-1-B-b) are obtained: Ex. No. X Y Z D A B R¹ m. p. ° C. IsomerI-1-A-b-1 4-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ 226 βI-1-A-b-2 4-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂—

209 β I-1-A-b-3 4-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂—

226 β I-1-A-b-4 4-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂—

231 β

Example No. I-1-A-c-1

0.42 ml (3 mmol) of triethylamine is added to 1.21 g of the compound ofExample I-1-A-a-4 in 30 ml of anhydrous dichloromethane (CH₂Cl₂). At10-20° C., 0.3 ml (3 mmol) of ethyl chloroformate in 3 ml of anhydrousCH₂Cl₂ is added dropwise.

The mixture is stirred at room temperature. The end of the reaction isdetermined by thin-layer chromatography.

The solvent is evaporated using a rotary evaporator and the residue istaken up in dichloromethane, washed twice with 20 ml of 0.5 N NaOH,dried and concentrated using a rotary evaporator. The residue ispurified by silica gel column chromatography (dichloromethane/ethylacetate, 3:1).

Yield: 0.4 g (29% of theory), m.p. 174° C.

Analogously to Examples (I-1-A-c-1) and (I-1-B-c-1), and in accordancewith the general statements about the preparation, the followingcompounds of the formulae (I-1-A-c) and (I-1-B-c) (I-1-A-c)

(I-1-B-c) are obtained: Ex. No. X Y Z D A B M R² m. p. ° C. IsomerI-1-A-c-2 4-Cl—C₆H₄ H C₃H₇ H —(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅ 157 βI-1-A-c-3 4-Cl—C₆H₄ H CH₃ H —(CH₂)₂—O—(CH₂)₂— O C₂H₅ 156 — I-1-A-c-44-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— O C₆H₅—CH₂ 167 β I-1-A-c-54-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— O C₂H₅ β

Example No. I-1-B-c-1

0.28 ml (2 mmol) of triethylamine is added to 1.21 g of the compound ofExample I-1-B-a-1 in 20 ml of anhydrous CH₂Cl₂. At 10-20° C., 0.2 ml (2mmol) of ethyl chloroformate in 3 ml of anhydrous CH₂Cl₂ is addeddropwise.

The mixture is stirred at room temperature. The end of the reaction isdetermined by thin-layer chromatography.

The solvent is evaporated using a rotary evaporator and the residue istaken up in dichloromethane, washed twice with 20 ml of 0.5 N NaOH,dried and concentrated using a rotary evaporator. The residue ispurified by silica gel column chromatography (dichloromethane/ethylacetate, 2:1).

Yield: 0.84 g (88% of theory), m.p. 244° C.

Example No. II-A-1

6.08 g of methyl 4-methoxy-1-aminocyclohexanecarboxylate hydrochloridein 80 ml of absolute THF and 8 ml of triethylamine are stirred for 5minutes. 4.3 g of N-(5-methyl-3-phenyl)pyrazolylacetic acid are added,and the mixture is stirred at room temperature for 15 minutes. 4.4 ml oftriethylamine are then added, immediately followed by the dropwiseaddition of 1.12 ml of phosphorus oxychloride such that the solutionboils gently. The mixture is stirred under reflux for 30 minutes.

The reaction solution is added to 400 ml of ice-water, made alkalineusing 7 ml of triethylamine and extracted with dichloromethane. Theextract is dried and concentrated using a rotary evaporator.

The residue is purified by silica gel column chromatography(dichloromethane/acetone 5:1).

Yield: 5.28 g (68% of theory), m.p. 140° C.

Analogously to Example (II-A-1) and in accordance with the generalstatements about the preparation, the following compounds of theformulae (II-A) and (II-B) (II-A)

(II-B) are obtained: Ex. No. X Y Z D A B R⁸ m. p. ° C. Isomer II-A-23-Cl—C₆H₄ H CH₃ H CH₃ CH₃ CH₃ 133 — II-A-3 3-Cl—C₆H₄ H CH₃ H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 143 β II-A-4 C₆H₅ H CH₃ H CH₃ CH₃ CH₃ 99  —II-A-5 4-Cl—C₆H₄ H CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 150 β II-A-64-Cl—C₆H₄ H CH₃ H —CH₂—O—(CH₂)₃— CH₃ 155 — II-A-7 4-Cl—C₆H₄ H CH₃ H—(CH₂)₂—O—(CH₂)₂— CH₃ 169 — II-A-8 4-Cl—C₆H₄ H CH₃ H CH₃ CH₃ CH₃ —II-A-9 4-Cl—C₆H₄ H CH₃ —(CH₂)₄— H C₂H₅ 107 — II-A-10 4-Cl—C₆H₄ H CH₃—(CH₂)₂—S—CH₂— H C₂H₅ 134 — II-A-11 4-Cl—C₆H₄ H CH₃ i-C₃H₇ H H C₂H₅ —II-A-12 4-Cl—C₆H₄ H C₂H₅ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 155 β II-A-134-Cl—C₆H₄ H C₃H₇ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 127 β II-A-14 3-CF₃—C₆H₄ HCH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 138 β II-A-15 3,4-Cl₂—C₆H₃ H CH₃ H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 151 β II-A-16 3-Br—C₆H₄ H CH₃ H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 149 β II-A-17 4-Cl—C₆H₄ H C₂H₅ H CH₃ CH₃ CH₃120 — II-A-18 4-Cl—C₆H₄ H C₃H₇ H CH₃ CH₃ CH₃ 151 — II-A-19 3-CF₃—C₆H₄ HCH₃ H CH₃ CH₃ CH₃ 268 — II-A-20 3,4-Cl₂—C₆H₃ H CH₃ H CH₃ CH₃ CH₃ 166 —II-A-21 3-Br—C₆H₄ H CH₃ H CH₃ CH₃ CH₃ 145 — II-A-22 4-Br—C₆H₄ H CH₃ H—(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 142 β II-A-23 4-Br—C₆H₄ H CH₃ H CH₃ CH₃ CH₃149 — II-A-24 4-Cl—C₆H₄ H CH₃

H H C₂H₅ oil — II-B-1 4-Cl—C₆H₄ CH₃ CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 160β II-B-2 2,4,6-Cl₃—C₆H₂ CH₃ CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 167 βII-B-3 3-CF₃—C₆H₄ CH₃ CH₃ H —(CH₂)₂—CHOCH₃—(CH₂)₂— CH₃ 125 β II-B-44-Cl—C₆H₄ CH₃ CH₃ CH₃ H CH₃ CH₃ CH₃ 155 —

Example No. I-2-A-a-1

1.9 g (4.5 mmol) of the compound of Example III-A-1 are dissolved in 5ml of DMF. With ice-cooling, 5.35 ml of a 1 molar potassiumtert-butoxide solution are added, the mixture is stirred at roomtemperature for 8 h and the solvent is then removed using a rotaryevaporator. The residue is dissolved in water, slowly acidified withconcentrated HCl, filtered off with suction and dried.

Yield: 1.01 g (24% of theory), log P (pH 2.3) 2.05

Analogously to Example (I-2-A-a-1) and in accordance with the generalstatements about the preparation, the following compounds of the formula(I-2-A-a) (I-2-A-a)

are obtained: logP Ex. No. X Y Z A B (pH 2.3) I-2-A-a-2 4-Cl—C₆H₄ H CH₃—(CH₂)₂—CHCF₃—(CH₂)₂— 2.74 I-2-A-a-3 4-Cl—C₆H₄ H CH₃ CH₃ CH₃ 1.74I-2-A-a-4 4-Cl—C₆H₄ H CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— 2.46 I-2-A-a-54-Cl—C₆H₄ H CH₃

2.35 I-2-A-a-6 4-Cl—C₆H₄ H CH₃ —CH₂—O—(CH₂)₃— 1.49 I-2-A-a-7 4-Cl—C₆H₄ HCH₃ —(CH₂)₂—O—(CH₂)₂— 1.55 I-2-A-a-8 4-Br—C₆H₄ H CH₃ C₂H₅ CH₃ 2.70I-2-A-a-9 C₆H₅ H CH₃ i-C₃H₇ CH₃ 1.50 I-2-A-a-10 3-CF₃—C₆H₄ H CH₃(CH₃)₃—C—CH₂ CH₃ 2.92

The log P values given for the Examples (I-2-A-a) were deterrnined inaccordance with EEC Directive 79/831 Annex V.A 8 by HPLC (HighPerformance Liquid Chromatography) using a reversed-phase column (C 18).Temperature: 43° C.

(a) Mobile phases for the determination in the acidic range: 0.1%aqueous phosphoric acid, acetonitrile; linear gradient from 10%acetonitrile to 90% acetonitrile.

(b) Mobile phases for the determination in the neutral range: 0.01 molaraqueous phosphate buffer solution, acetonitrile; linear gradient from10% acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (of 3 to 16carbon atoms) with known log P values (determination of the log P valuesby the retention times using linear interpolation between two successivealkanones).

The lambda max values were determined in the maxima of thechromatographic signals using the UV spectra from 200 nm to 400 nm.

Example No. I-2-A-b-1

With ice-cooling, 0.074 g (0.61 nmnol) of pivaloyl chloride is added to0.2 g (0.554 nmmol) of the compound of Preparation Example I-2-A-a-6 in10 ml of anhydrous dichloromethane and 0.062 g (0.61 mmol) oftriethylamine, and the mixture is stirred at room temperature for 8hours.

The reaction solution is washed with 10% citric acid and 10% NaOHsolution, the organic phase is separated off and dried and the solventis distilled off.

Yield: 0.141 g (50.4% of theory), log P (pH 2.3) 4.32.

Example No. III-A-1

0.9 g (4.5 mmol) of ethyl 4-methoxy-1-hydroxycyclohexanecarboxylate and1.2 g (4.5 mmol) of the compound of Example XVI-A-1 are stirred at 140°C. for 6 hours and then cooled, and the HCl gas is removed using astream of argon.

Yield: 1.93 g (99% of theory), log P (pH 2.3) 4.11.

Analogously to Example (III-A-1) and in accordance with the generalstatements about the preparation, the following compounds of the formula(III-A) (III-A)

are obtained: Ex. No. X Y Z A B R m. p. ° C. III-A-2 4-Cl—C₆H₄ H CH₃—(CH₂)₂—CHCF₃—(CH₂)₂— C₂H₅ *1 III-A-3 4-Cl—C₆H₄ H CH₃ CH₃ CH₃ C₂H₅ *1III-A-4 4-Cl—C₆H₄ H CH₃ —(CH₂)₂—CHOC₂H₅—(CH₂)₂— C₂H₅ *1 III-A-54-Cl—C₆H₄ H CH₃

C₂H₅ *1 III-A-6 4-C—C₆H₄ H CH₃ —CH₂—O—(CH₂)₃— C₂H₅ *1 III-A-7 4-C—C₆H₄ HCH₃ —(CH₂)₂—O—(CH₂)₂— C₂H₅ *1 III-A-8 4-Br—C₆H₄ H CH₃ C₂H₅ CH₃ C₂H₅ *1III-A-9 C₆H₅ H CH₃ i-C₃H₇ CH₃ C₂H₅ *1 III-A-10 3-CF₃—C₆H₄ H CH₃(CH₃)₃—C—CH₂ CH₃ C₂H₅ *1*1 The compounds were used as crude products for preparing compounds ofthe formula (I-2-A-a).

Example No. XVI-A-1

With ice-cooling, 4.4 g (34.7 rnnol) of oxalyl chloride are slowly addeddropwise to 5.89 g (23 mmol) of the compound of Example XIX-A-1 inCH₂Cl₂. The mixture is stirred at room temperature for 8 h and thenunder reflux for 2 h. The solvent is removed under reduced pressure.

Yield: 6.22 g (96% of theory)

Example No. XIX-A-1

10.7 g (0.04 mol) of the compound of Example XXIV-A-1 are dissolved in20 ml of methanol, and 3.36 g (0.08 mol) of potassium hydroxide in 13 mlof water are added. The mixture is stirred at room temperature for 8 h.The solvent is removed using a rotary evaporator and the residue isstirred with water and adjusted to pH 2 using concentrated hydrochloricacid. The precipitate is filtered off with suction and dried.

Yield: 7.28 g (72% of theory), m.p. 200° C.-203° C.

Analogously to Example (XIX-A-1), the following compounds of the formula(XIX-A) (XIX-A)

are obtained: Ex. No. X Y Z m. p. ° C. XVII-A-2 4-Cl—C₆H₄ H C₂H₅ 188XVII-A-3 4-Cl—C₆H₄ H C₃H₇ 181 XVII-A-4 3-Br—C₆H₄ H CH₃ 209 XVII-A-54-Br—C₆H₄ H CH₃ 219 XVII-A-6 3-CF₃—C₆H₄ H CH₃ 202 XVII-A-7 3,4-Cl₂—C₆H₃H CH₃ 220 XVII-A-8 3-Cl—C₆H₄ H CH₃ 206-207 XVII-A-9 3-CF₃—C₆H₄ H CH₃200-201 XVII-A-10 C₆H₅ H CH₃ 173-175

Example No. XXIV-A-1

12.76 g (0.083 mol) of methyl bromoacetate are added to 14 g (0.073 mol)of 3-(4-chlorphenyl)-5-methylpyrazole and 11.5 g (0.083 mol) ofpotassium carbonate in 209 ml of acetonitrile. The mixture is stirred at50° C. for 26 h. After cooling, the inorganic salts are filtered off,methylene chloride is added, the mixture is washed with saturated NaHCO₃solution and dried and the solvent is removed using a rotary evaporator.

The product is purified by silica gel column chromatography(dichloromethane/methanol 99:1).

Yield: 10.7 g (55.5% of theory), m.p. 81-83° C.

Analogously to Example (XXIV-A-1), the following compounds of theformula (XXIV-A) (XXIV-A)

are obtained: Ex. No. X Y Z R⁸ m. p. ° C. XXIV-A-2 4-Cl—C₆H₄ H C₂H₅ CH₃*1 XXIV-A-3 4-Cl—C₆H₄ H C₃H₇ CH₃ *1 XXIV-A-4 3-Br—C₆H₄ H CH₃ CH₃ *1XXIV-A-5 4-Br—C₆H₄ H CH₃ CH₃ *1 XXIV-A-6 3-CF₃—C₆H₄ H CH₃ CH₃ *1XXIV-A-7 3,4-Cl₂—C₆H₃ H CH₃ CH₃ *1 XXIV-A-8 3-Cl—C₆H₄ H CH₃ CH₃ oilXXIV-A-9 4-CF₃—C₆H₄ H CH₃ CH₃ 116 XXIV-A-10 C₆H₅ H CH₃ CH₃ oil*1 The compounds were used as crude material for preparing the compoundsof the formula (XVII-A).

Compound of the formula XXW-A-4

¹H-NMR 400 MHz (CDCl₃): δ=2.3 (s, 3H), 3.9 (s, 3H), 4.9 (s, 2H), 6.3 (s,1H), 7.3 (m, 1H), 7.4 (m, 1H), 8.0 (s, 1H).

Compound of the formula XXIV-A-5

MS (CJ) m/e: 308, 310

Compound of the formula XXIV-A-6

¹H-NMR 400 MHz, (CDCl₃): δ=2.1 (s, 3H) 4.9 (s, 2H), 6.4 (s, 1H), 7.75 to7.9 (m, 3H), 8.2 (s, 1H).

Compound of the formula XXIV-A-7

¹H-NMR 400 MHz, (CDCl₃): δ=2.1 (s, 3H), 3.8 (s, 3H), 6.3 (s, 1H), 7.4(m, 1H), 7.55 (m, 1H), 7.9 (s, 1H).

Example

6 g of hydrazine hydrate are added to 15 g (0.077 mol) of4-chlorobenzoylacetone in 40 ml of ethanol, and the mixture is stirredunder reflux for 8 h. The precipitate is filtered off with suction,washed with water and dried.

Yield: 14 g (94% of theory), m.p. 154 to 156° C.

Example A

Aphis gossypii Test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cotton leaves (Gossypium hirsutum) which are heavily infested by thecotton aphid (Aphis gossypii) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed.

In this test, for example, the following compound of the PreparationExamples shows good activity: TABLE A plant-damaging insects Aphisgossipii test Concentration of active Kill rate in Active compoundscompound in ppm % after 6^(d) Example I-1-A-a-4 500 95

Example B

Myzus Test Solvent: 7 parts by weight of dimethylformamide Emulsifier: 1part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) which are heavily infested by thepeach aphid (Myzus persicae) are treated by being dipped into thepreparation of active compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshave been killed.

In this test, for example, the following compounds of the PreparationExamples show good activity: TABLE B plant-damaging insects Myzus testConcentration of active Kill rate in Active compounds compound in ppm %after 6^(d) Example I-2-A-a-1 500 90 Example I-1-A-a-4 500 90

Example C

Phaedon Larvae Test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, for example, the following compounds of the PreparationExamples show good activity: TABLE C plant-damaging insects Phaedonlarvae test Concentration of active Kill rate in Active compoundscompound in ppm % after 7^(d) Example I-1-A-a-4 500 100 ExampleI-1-A-c-1 500 90

Example D

Plutella Test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the diamondback moth (Plutellaxylostella) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, for example, the following compound of the PreparationExample shows good activity: TABLE D plant-damaging insects Plutellatest Concentration of active Kill rate in Active compounds compound inppm % after 7^(d) Example I-1-A-a-4 500 100

Example E

Spodoptera frugiperda Test Solvent: 7 parts by weight ofdimethylformamide Emulsifier: 2 parts by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the armyworm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, for example, the following compounds of the PreparationExample show good activity: TABLE E plant-damaging insects Spodopterafrugiperda test Concentration of active Kill rate in Active compoundscompound in ppm % after 7^(d) Example I-1-A-a-4 500 100 ExampleI-1-A-c-1 500 100

Example F

Tetranychus Test (OP-Resistant/Dip Treatment) Solvent: 7 parts by weightof dimethylformamide Emulsifier: 2 parts by weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by allstages of the greenhouse red spider mite (Tetranychus urticae) aretreated by being dipped into a preparation of active compound of thedesired concentration.

After the desired period of time, the effect in % is determined. 100%means that all spider mites have been killed; 0% means that none of thespider mites have been killed.

In this test, for example, the following compounds of the PreparationExamples show good activity: TABLE F plant-damaging mites Tetranychustest (OP-resistant/dip treatment) Concentration of active Kill rate inActive compounds compound in ppm % after 7^(d) Example I-2-A-a-1 100 100Example I-1-A-a-4 100 95 Example I-1-A-c-1 100 98

Example G

Post-Emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants of a height of 5-15 cm are sprayed with the preparation ofactive compound such that the particular amounts of active compounddesired are applied per unit area. The concentration of the spray liquoris chosen such that the particular amounts of active compound desiredare applied in 1000 l of water/ha.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control.

The figures denote:  0% = no effect (like untreated control) 100% =total destruction

Example H

Pre-Emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours,the soil is sprayed with the preparation of active compound such thatthe particular amounts of active compound are applied per unit area. Theconcentration of the spray liquor is chosen such that the particularamounts of active compound desired are applied in 1000 l of water/ha.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control.

The figures denote:  0% = no effect (like untreated control) 100% =total destruction

Pyrazolyl-substituted heterocycles post-emergence/greenhouse g ai/haAlopecurus Avena fatua Setaria Amaranthus Ex. I-1-B-c-1 2000 90 90 95 90post-emergence/greenhouse g ai/ha Alopecurus Avena fatua SetariaAbutilon Amaranthus Sinapis Ex. I-1-A-c-1 250 100 100 100 95 95 80post-emergence/greenhouse g ai/ha Sugarbeet Alopecurus Avena fatuaBromus Lolium Setaria Abutilon Ex. I-1-A-a-4 250 10 100 100 100 100 10080 post-emergence/greenhouse g ai/ha Oilseed rape Alopecurus Avena fatuaBromus Lolium Setaria Viola Ex. I-1-A-a-4 125 0 100 100 100 100 100 100

Example I

Critical Concentration Test/Soil Insects—Treatment of Transgenic PlantsTest insect: Diabrotica balteata - larvae in soil Solvent: 7 parts byweight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil. Here, theconcentration of active compound in the preparation is virtuallyimmaterial, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled into0.25 l pots, and these are allowed to stand at 20° C.

Immediately after the preparation, 5 pregerminated maize corns of thecultivar YIELD GUARD (trademark of Monsanto Comp., USA) are placed intoeach pot. After 2 days, the appropriate test insects are placed into thetreated soil. After a further 7 days, the efficacy of the activecompound is determined by counting the maize plants that have emerged (1plant=20% activity).

Example J

Heliothis virescens Test—Treatment of Transgenic Plants Solvent: 7 partsby weight of acetone Emulsifier: 1 part by weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trademarkof Monsanto Comp., USA) are treated by being dipped into the preparationof active compound of the desired concentration and are populated withthe tobacco budworm Heliothis virescens while the leaves are stillmoist.

After the desired period of time, the kill of the insects is determined.

1-17. (canceled)
 18. A compound of formula (I-1-B), (I-2-A), (I-2-B),(I-3-A), or (I-3-B)

in which X represents optionally substituted phenyl or hetaryl, Yrepresents hydrogen or alkyl, Z represents alkyl, halogen, hydroxyl,alkoxy, or haloalkoxy; or represents optionally substitutedphenylalkyloxy, hetarylalkyloxy, or cycloalkyl, A represents hydrogen;represents optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,polyalkoxyalkyl, or alkylthioalkyl; represents saturated or unsaturated,optionally substituted cycloalkyl in which one or more ring atom isoptionally replaced by a heteroatom; or represents optionally halogen-,alkyl-, haloalkyl-, alkoxy-, haloalkoxy-, cyano-, or nitro-substitutedaryl, arylalkyl, or hetaryl, B represents hydrogen, alkyl, oralkoxyalkyl, or A and B together with the carbon atom to which they areattached represent a saturated or unsaturated, unsubstituted orsubstituted cycle that optionally contains one or more heteroatoms, Drepresents hydrogen; represents optionally substituted alkyl, alkenyl,alkynyl, alkoxyalkyl, polyalkoxyalkyl, or alkylthioalkyl; representssaturated or unsaturated cycloalkyl in which one or more ring atoms areoptionally replaced by heteroatoms; or represents optionally substitutedarylalkyl, aryl, hetarylalkyl, or hetaryl, or A and D together with theatoms to which they are attached represent a saturated or unsaturatedcycle that is unsubstituted or substituted in the A,D moiety andoptionally contains one or more heteroatoms, and G represents hydrogen(a) or represents one of the groups

in which E represents a metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,alkylthioalkyl, or polyalkoxyalkyl; represents optionally halogen-,alkyl-, or alkoxy-substituted cycloalkyl that is optionally interruptedby one or more heteroatoms; or represents optionally substituted phenyl,phenylalkyl, hetaryl, phenoxyalkyl, or hetaryloxyalkyl, R² representsoptionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, orpolyalkoxyalkyl; or represents optionally substituted cycloalkyl,phenyl, or benzyl, R³ represents alkyl, haloalkyl or representsoptionally substituted phenyl or benzyl, R⁴ and R⁵ independently of oneanother represent optionally halogen-substituted alkyl, alkoxy,alkylamino, dialkylamino, alkylthio, alkenylthio, or cycloalkylthio; orrepresent optionally substituted phenyl, benzyl, phenoxy, or phenylthio,and R⁶ and R⁷ independently of one another represent hydrogen; representoptionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, oralkoxyalkyl; represent optionally substituted phenyl; or representoptionally substituted benzyl; or R⁶ and R⁷ together with the N atom towhich they are attached represent a cycle that is optionally interruptedby oxygen or sulphur.
 19. A compound according to claim 18 in which Xrepresents optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,C₁-C₄-haloalkyl-, C₁-C₄-haloalkoxy-, nitro-, or cyano-substituted phenylor 5- or 6-membered hetaryl, Y represents hydrogen, halogen, orC₁-C₆-alkyl, Z represents C₁-C₆-alkyl, halogen, hydroxyl, C₁-C₆-alkoxy,or C₁-C₆-haloalkoxy; represents optionally C₁-C₆-alkyl-, C₁-C₆-alkoxy-,halogen-, C₁-C₄-haloalkyl-, C₁-C₆-haloalkoxy-, cyano-, ornitro-substituted phenyl-C₁-C₂-alkoxy or hetaryl-C₁-C₂-alkoxy; orrepresents optionally C₁-C₂-alkyl- or halogen-substitutedC₃-C₆-cycloalkyl, A represents hydrogen; represents optionally fluorine-or chlorine-substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl,C₁-C₁₀-alkoxy-C₁-C₈-alkyl, poly-C₁-C₈-alkoxy-C₁-C₈-alkyl, orC₁-C₁₀-alkylthio-C₁-C₆-alkyl; represents optionally fluorine-,chlorine-, C₁-C₆-alkyl-, or C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl inwhich one or two ring members that are not directly adjacent areoptionally replaced by oxygen and/or sulphur; or represents optionallyhalogen-, C₁-C₆-alkyl-, C₁-C₆-haloalkyl-, C₁-C₆-alkoxy-,C₁-C₆-haloalkoxy-, cyano-, or nitro-substituted C₆- or C₁₀-aryl, hetarylhaving 5 or 6 ring atoms, or C₆- or C₁₀-aryl-C₁-C₆-alkyl, B representshydrogen, C₁-C₁₂-alkyl or C₁-C₈-alkoxy-C₁-C₆-alkyl, or A, B, and thecarbon atom to which they are attached represent saturatedC₃-C₁₀-cycloalkyl or unsaturated C₅-C₁₀-cycloalkyl in which one ringmember is optionally replaced by oxygen or sulphur and that isoptionally mono- or disubstituted by C₁-C₈-alkyl, C₃-C₁₀-cycloalkyl,C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen, or phenyl, orA, B, and the carbon atom to which they are attached representC₅-C₆-cycloalkyl that is substituted by an alkylenediyl group thatoptionally contains one or two oxygen and/or sulphur atoms that are notdirectly adjacent or by an alkylene-dioxyl or an alkylenedithioyl groupwhich, together with the carbon atom to which it is attached, forms afurther five- to eight-membered ring that is optionally substituted byC₁-C₄-alkyl, or A, B, and the carbon atom to which they are attachedrepresent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which twosubstituents together with the carbon atoms to which they are attachedrepresent optionally C₁-C₆-alkyl-, C₁-C₆-alkoxy-, or halogen-substitutedC₂-C₆-alkanediyl, C₂-C₆-alkenediyl, or C₄-C₆-alkane-dienediyl in whichone methylene group is optionally replaced by oxygen or sulphur, Drepresents hydrogen; represents optionally halogen-substitutedC₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl,poly-C₁-C₈-alkoxy-C₂-C₈-alkyl, or C₁-C₁₀-alkylthio-C₂-C₈-alkyl;represents optionally halogen-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, orC₁-C₄-haloalkyl-substituted C₃-C₈-cycloalkyl in which one ring member isoptionally replaced by oxygen or sulphur; or represents optionallyhalogen-, C₁-C₆-alkyl-, C₁-C₆-haloalkyl-, C₁-C₆-alkoxy-,C₁-C₆-haloalkoxy-, cyano-, or nitro-substituted phenyl, hetaryl having 5or 6 ring atoms, phenyl-C₁-C₆-alkyl, or hetaryl-C₁-C₆-alkyl having 5 or6 ring atoms, or A and D together represent optionally substitutedC₃-C₆-alkanediyl or C₃-C₆-alkenediyl in which one methylene group isoptionally replaced by a carbonyl group, oxygen, or sulphur, where theoptional substituents are halogen, hydroxyl, or mercapto, or optionallyhalogen-substituted C₁-C₁₀-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio,C₃-C₇-cycloalkyl, phenyl, or benzyloxy, or a further C₃-C₆-alkanediylgrouping, C₃-C₆-alkenediyl grouping, or a butadienyl grouping that isoptionally substituted by C₁-C₆-alkyl, or in which two adjacentsubstituents together with the carbon atoms to which they are attachedoptionally form a further saturated or unsaturated cycle having 5 or 6ring atoms and optionally containing oxygen or sulphur, and G representshydrogen (a) or represents one of the groups

in which E represents a metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents optionally halogen-substituted C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl, orpoly-C₁-C₈-alkoxy-C₁-C₈-alkyl; or represents optionally halogen-,C₁-C₆-alkyl-, or C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl in which oneor more ring members that are not directly adjacent are optionallyreplaced by oxygen and/or sulphur; represents optionally halogen-,cyano-, nitro-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-, C₁-C₆-haloalkyl-,C₁-C₆-haloalkoxy-, C₁-C₆-alkylthio-, or C₁-C₆-alkylsulphonyl-substitutedphenyl; represents optionally halogen-, nitro-, cyano-, C₁-C₆-alkyl-,C₁-C₆-alkoxy-, C₁-C₆-haloalkyl-, or C₁-C₆-haloalkoxy-substitutedphenyl-C₁-C₆-alkyl; represents optionally halogen-, C₁-C₆-alkyl-,C₁-C₂-haloalkyl-, or C₁-C₄-alkoxy-substituted 5- or 6-membered hetaryl;represents optionally halogen- or C₁-C₆-alkyl-substitutedphenoxy-C₁-C₆-alkyl; or represents optionally halogen-, amino-, orC₁-C₆-alkyl-substituted 5- or 6-membered hetaryloxy-C₁-C₆-alkyl, R²represents optionally halogen-substituted C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₁-C₈₋alkoxy-C₂-C₈-alkyl, or poly-C₁-C₈-alkoxy-C₂-C₈-alkyl; representsoptionally halogen-, C₁-C₆-alkyl-, or C₁-C₆-alkoxy-substitutedC₃-C₈-cycloalkyl in which one ring atom is optionally replaced byoxygen; or represents optionally halogen-, cyano-, nitro-, C₁-C₆-alkyl-,C₁-C₆-alkoxy-, C₁-C₆-haloalkyl-, or C₁-C₆-haloalkoxy-substituted phenylor benzyl, R³ represents optionally halogen-substituted C₁-C₈-alkyl; orrepresents optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,C₁-C₄-haloalkyl-, C₁-C₄-haloalkoxy-, cyano-, or nitro-substituted phenylor benzyl, R⁴ and R⁵ independently of one another represent optionallyhalogen-substituted C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino,di(C₁-C₈-alkyl)amino, C₁-C₈-alkylthio, C₂-C₈-alkenylthio, orC₃-C₇-cycloalkyl-thio; or represent optionally halogen-, nitro-, cyano-,C₁-C₄-alkoxy-, C₁-C₄-haloalkoxy-, C₁-C₄-alkylthio-,C₁-C₄-haloalkylthio-, C₁-C₄-alkyl-, or C₁-C₄-haloalkyl-substitutedphenyl, phenoxy or phenylthio, and R⁶ and R⁷ independently of oneanother represent hydrogen; represent optionally halogen-substitutedC₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl, orC₁-C₈-alkoxy-C₁-C₈-alkyl; represent optionally halogen-,C₁-C₈-haloalkyl-, C₁-C₈-alkyl-, or C₁-C₈-alkoxy-substituted phenyl; orrepresent optionally halogen-, C₁-C₈-alkyl-, C₁-C₈-haloalkyl-, orC₁-C₈-alkoxy-substituted benzyl; or R⁶ and R⁷ together represent anoptionally C₁-C₄-alkyl-substituted C₃-C₆-alkylene radical in which onecarbon atom is optionally replaced by oxygen or sulphur.
 20. A compoundaccording to claim 18 in which X represents phenyl, pyridyl, pyrimidyl,or thiazolyl, each of which is optionally mono- to trisubstituted byfluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-haloalkyl,C₁-C₂-haloalkoxy, nitro, or cyano, Y represents hydrogen, chlorine,bromine, or C₁-C₄-alkyl, Z represents C₁-C₄-alkyl, chlorine, bromine,C₁-C₄-alkoxy, or C₁-C₄-haloalkoxy; or represents benzyloxy or hetaryloxyhaving 5 or 6 ring atoms, each of which radicals is optionally mono- ordisubstituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, fluorine, chlorine, bromine,C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, cyano, or nitro, A representshydrogen; represents optionally fluorine-substituted C₁-C₁₀-alkyl, orC₁-C₈-alkoxy-C₁-C₆-alkyl; represents optionally fluorine-, chlorine-,C₁-C₄-alkyl-, or C₁-C₄-alkoxy-substituted C₃-C₇-cycloalkyl in which onering member is optionally replaced by oxygen or sulphur; or representsphenyl or phenyl-C₁-C₂-alkyl, each of which is optionally substituted byfluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,cyano, nitro, or C₁-C₄-haloalkoxy, B represents hydrogen orC₁-C₁₀-alkyl, or A, B, and the carbon atom to which they are attachedrepresent saturated C₃-C₇-cycloalkyl or unsaturated C₅-C₇-cycloalkyl inwhich one ring member is optionally replaced by oxygen or sulphur andthat is optionally mono- or disubstituted by C₁-C₆-alkyl,C₅-C₈-cycloalkyl, C₁-C₃-haloalkyl, C₁-C₆-alkoxy, fluorine, chlorine, orphenyl, or A, B, and the carbon atom to which they are attachedrepresent C₅-C₆-cycloalkyl that is substituted by an alkylenediyl groupthat optionally contains one or two oxygen or sulphur atoms that are notdirectly adjacent or by an alkylenedioxyl or by an alkylenedithiolylgroup which, together with the carbon atom to which it is attached,forms a further five- or six-membered ring that is optionallysubstituted by C₁-C₃-alkyl, or A, B, and the carbon atom to which theyare attached represent C₅-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in whichtwo substituents together with the carbon atoms to which they areattached represent C₂-C₄-alkanediyl or C₂-C₄-alkenediyl in which onemethylene group is optionally replaced by oxygen or sulphur, each ofwhich radicals is optionally substituted by C₁-C₅-alkyl, C₁-C₅-alkoxy,fluorine, chlorine, or bromine, or represent butadienediyl, D representshydrogen; represents optionally fluorine-substituted C₁-C₁₀-alkyl,C₃-C₆-alkenyl, C₁-C₆-alkoxy-C₂-C₄-alkyl, or C₁-C₆-alkylthio-C₂-C₄-alkyl;represents optionally fluorine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, orC₁-C₂-haloalkyl-substituted C₃-C₇-cycloalkyl in which one methylenegroup is optionally replaced by oxygen or sulphur; or represents phenylor phenyl-C₁-C₄-alkyl, each of which is optionally substituted byfluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,or C₁-C₄-haloalkoxy, or A and D together represent optionallysubstituted C₃-C₅-alkanediyl in which one methylene group is optionallyreplaced by oxygen or sulphur, where the optional substituents areC₁-C₆-alkyl and C₁-C₄-alkoxy, or, for compounds of formula (I-1) inwhich G is group (1), A and D together with the atoms to which they areattached represent one of the groups AD-1 to AD-10

G represents hydrogen (a) or represents one of the groups

in which E represents a metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents optionally fluorine- or chlorine-substituted C₁-C₁₆-alkyl,C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₄-alkyl, orC₁-C₆-alkylthio-C₁-C₄-alkyl; represents optionally fluorine-, chlorine-,C₁-C₅-alkyl-, or C₁-C₅-alkoxy-substituted C₃-C₇-cycloalkyl in which oneor two ring members that are not directly adjacent are optionallyreplaced by oxygen and/or sulphur; represents optionally fluorine-,chlorine-, bromine-, cyano-, nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-,C₁-C₃-haloalkyl-, C₁-C₃-halo-alkoxy-, C₁-C₄-alkylthio-, orC₁-C₄-alkylsulphonyl-substituted phenyl; represents optionallyfluorine-, chlorine-, bromine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-,C₁-C₃-haloalkyl-, or C₁-C₃-haloalkoxy-substituted phenyl-C₁-C₄-alkyl; orrepresents optionally fluorine-, chlorine-, bromine-, C₁-C₄-alkyl-,trifluoromethyl-, or C₁-C₂-alkoxy-substituted pyrazolyl, thiazolyl,pyridyl, pyrimidyl, furanyl, or thienyl, R² represents optionallyfluorine-substituted C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, orC₁-C₆-alkoxy-C₂-C₆-alkyl; represents optionally fluorine-, chlorine-,C₁-C₄-alkyl-. or C₁-C₄-alkoxy-substituted C₃-C₇-cycloalkyl; orrepresents optionally fluorine-, chlorine-, bromine-, cyano-, nitro-,C₁-C₄-alkyl-, C₁-C₃-alkoxy-, C₁-C₂-haloalkyl-, orC₁-C2-haloalkoxy-substituted phenyl or benzyl, R³ represents optionallyfluorine-substituted C₁-C₆-alkyl; or represents optionally fluorine-,chlorine-, bromine-, C₁-C₄-alkyl-, C₁-C₄-alkoxy-, C₁-C₃-haloalkyl-,C₁-C₃-haloalkoxy-, cyano-, or nitro-substituted phenyl, R⁴ representsC₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylamino, di(C₁-C₆-alkyl)amino,C₁-C₆-alkylthio, C₃-C₄-alkenylthio, or C₃-C₆-cycloalkylthio; orrepresents optionally fluorine-, chlorine-, bromine-, nitro-, cyano-,C₁-C₃-alkoxy-, C₁-C₃-haloalkoxy-, C₁-C₃-alkylthio-,C₁-C₃-haloalkylthio-, C₁-C₃-alkyl-, or C₁-C₃-haloalkyl-substitutedphenyl, phenoxy, or phenylthio, R⁵ represents C₁-C₆-alkoxy orC₁-C₆-alkylthio, R⁶ represents C₁-C₆-alkyl, C₃-C₆-cycloalkyl,C₁-C₆-alkoxy, C₃-C₆-alkenyl, or C₁-C₆-alkoxy-C₁-C₆-alkyl; representsoptionally fluorine-, chlorine-, bromine-, C₁-C₃-haloalkyl-,C₁-C₄-alkyl-, or C₁-C₄-alkoxy-substituted phenyl; represents optionallyfluorine-, chlorine-, bromine-, C₁-C₄-alkyl-, C₁-C₃-haloalkyl-, orC₁-C₄-alkoxy-substituted benzyl, and R⁷ represents hydrogen,C₁-C₆-alkyl, C₃-C₆-alkenyl, or R⁶ and R⁷ together represent anoptionally methyl- or ethyl-substituted C₄-C₅-alkylene radical in whichone methylene group is optionally replaced by oxygen or sulphur.
 21. Acompound according to claim 18 in which X represents phenyl that isoptionally mono- or disubstituted by fluorine, chlorine, bromine,methyl, ethyl, trifluoromethyl, isopropyl, tert-butyl, trifluoromethoxy,methoxy, ethoxy, isopropoxy, tert-butoxy, cyano, or nitro, Y representshydrogen, methyl, or ethyl, Z represents methyl, ethyl, propyl,isopropyl, chlorine, methoxy, ethoxy, propoxy, isopropoxy,difluoromethoxy, or trifluoroethoxy, A represents hydrogen; representsoptionally fluorine-substituted C₁-C₈-alkyl, orC₁-C₆-alkoxy-C₁-C₄-alkyl; represents optionally fluorine-, methyl-,ethyl-, or methoxy-substituted C₃-C₆-cycloalkyl in which one ring memberis optionally replaced by oxygen or sulphur; or represents phenyl orbenzyl, each of which is optionally mono- or disubstituted by fluorine,chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy,trifluoromethyl, trifluoromethoxy, cyano, or nitro, B representshydrogen or C₁-C₆-alkyl, or A, B, and the carbon atom to which they areattached represent saturated C₃-C₆-cycloalkyl in which one ring memberis optionally replaced by oxygen or sulphur and that is optionallymonosubstituted by methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, trifluoromethyl, methoxy, ethoxy, propoxy,isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, fluorine, orchlorine, or A, B, and the carbon atom to which they are attachedrepresent C₆-cycloalkyl that is substituted by an alkylenedioxyl groupthat is optionally mono- or disubstituted by methyl or ethyl and which,together with the carbon atom to which it is attached, forms a furtherfive- or six-membered ring, or A, B, and the carbon atom to which theyare attached represent C₅-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in whichtwo substituents together with the carbon atoms to which they areattached represent C₂-C₄-alkanediyl or C₂-C₄-alkenediyl in which onemethylene group is optionally replaced by oxygen or sulphur, orrepresent butadienediyl, D represents hydrogen; represents optionallyfluorine-substituted C₁-C₈-alkyl, C₃-C₄-alkenyl,C₁-C₆-alkoxy-C₂-C₄-alkyl, or C₁-C₄-alkylthio-C₂-C₄-alkyl; or representstrifluoromethyl- or fluorine-substituted C₃-C₆-cycloalkyl in which onemethylene group is optionally replaced by oxygen or sulphur; orrepresents phenyl or benzyl, each of which is optionally mono- ordisubstituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl,methoxy, ethoxy, trifluoromethyl, or trifluoromethoxy, or A and Dtogether represent C₃-C₄-alkanediyl in which one carbon atom isoptionally replaced by sulphur and that is optionally mono- ordisubstituted by methyl, ethyl, methoxy, or ethoxy, or, for compounds offormula (I-1) in which G is group (1), A and D together with the atomsto which they are attached represent one of the groups AD below:

G represents hydrogen (a) or represents one of the groups

in which E represents a metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents optionally fluorine- or chlorine-substituted C₁-C₁₄-alkyl,C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₂-alkyl, orC₁-C₄-alkylthio-C₁-C₂-alkyl; represents C₃-C₆-cycloalkyl that isoptionally mono- or disubstituted by fluorine, chlorine, methyl, ethyl,propyl, isopropyl, butyl, isobutyl, tert-butyl, methoxy, or ethoxy andin which one or two ring members that are not directly adjacent areoptionally replaced by oxygen and/or sulphur; represents phenyl that isoptionally mono- or disubstituted by fluorine, chlorine, bromine, cyano,nitro, methyl, ethyl, n-propyl, i-propyl, tert-butyl, methoxy, ethoxy,i-propoxy, tert-butoxy, trifluoromethyl, or trifluoromethoxy; orrepresents furanyl, thienyl, or pyridyl, each of which is optionallymono- or disubstituted by fluorine, chlorine, bromine, methyl, or ethyl;R² represents C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, or C₁-C₄-alkoxy-C₂-C₆-alkyl,each of which is optionally mono- to trisubstituted by fluorine;represents C₃-C₆-cycloalkyl that is optionally mono- or disubstituted byfluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, or methoxy; orrepresents phenyl or benzyl, each of which is optionally mono- ordisubstituted by fluorine, chlorine, cyano, nitro, methyl, ethyl,n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, ortrifluoromethoxy, R³ represents methyl, ethyl, or n-propyl, each ofwhich is optionally mono- to trisubstituted by fluorine; or representsphenyl that is optionally mono- or disubstituted by fluorine, chlorine,bromine, methyl, tert-butyl, methoxy, trifluoromethyl, trifluoromethoxy,cyano, or nitro, R⁴ represents C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-alkylamino, di(C₁-C₄-alkyl)amino, or C₁-C₄-alkylthio; orrepresents phenyl, phenoxy, or phenylthio, each of which is optionallymono- or disubstituted by fluorine, chlorine, bromine, nitro, cyano,C₁-C₂-alkoxy, C₁-C₂-fluoroalkoxy, C₁-C₂-alkylthio,C₁-C₂-fluoroalkylthio, or C₁-C₃-alkyl, R⁵ represents methoxy, ethoxy,methylthio, or ethylthio, R⁶ represents C₁-C₄-alkyl, C₃-C₆-cycloalkyl,C₁-C₄-alkoxy, C₃-C₄-alkenyl, C₁-C₄-alkoxy-C₁-C₄-alkyl; represents phenylthat is optionally mono- or disubstituted by fluorine, chlorine,bromine, trifluoromethyl, methyl, or methoxy; represents benzyl that isoptionally mono- or disubstituted by fluorine, chlorine, bromine,methyl, trifluoromethyl, or methoxy, and R⁷ represents hydrogen, methyl,ethyl, propyl, or allyl, or R⁶ and R⁷ together represent aC₅-C₆-alkylene radical in which one methylene group is optionallyreplaced by oxygen or sulphur.
 22. A compound of formula (I-2-A) or(I-2-B) according to claim 18

in which X represents phenyl that is optionally mono- or disubstitutedby fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, ortrifluoromethoxy, Y represents hydrogen or methyl, Z represents methyl,ethyl, or propyl, and A represents hydrogen or C₁-C₆-alkyl, B representshydrogen or C₁-C₆-alkyl, or A, B, and the carbon atom to which they areattached represent saturated C₅-C₆-cycloalkyl in which one ring memberis optionally replaced by oxygen or sulphur and that is optionallymonosubstituted by methyl, ethyl, propyl, isopropyl, trifluoromethyl,methoxy, ethoxy, propoxy, isopropoxy, butoxy, or isobutoxy, or A, B, andthe carbon atom to which they are attached represent C₅-C₆-cycloalkyl orC₅-C₆-cycloalkenyl in which two substituents together with the carbonatoms to which they are attached represent butadienyl, D representshydrogen, methyl, ethyl, or isopropyl; or representstrifluoromethyl-substituted cyclohexyl, or A and D together representC₃-C₄-alkanediyl, and G represents hydrogen (a) or represents one of thegroups

in which L represents oxygen, M represents oxygen or sulphur, R¹represents C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₂-alkoxy-C₁-C₂-alkyl, orC₁-C₂-alkylthio-C₁-C₂-alkyl, each of which is optionally mono- totrisubstituted by fluorine or chlorine; or represents C₃-C₆-cycloalkylthat is optionally monosubstituted by fluorine, chlorine, methyl, ethyl,or methoxy and in which one ring member is optionally replaced by oxygenor sulphur; represents phenyl which is optionally mono-substituted byfluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl,i-propyl, tert-butyl, methoxy, ethoxy, i-propoxy, tert-butoxy,trifluoromethyl, or trifluoromethoxy; or represents thienyl or pyridyl,each of which is optionally monosubstituted by fluorine, chlorine,bromine, methyl, or ethyl, and R² represents C₁-C₆-alkyl, C₂-C₆-alkenyl,or C₁-C₄-alkoxy-C₂-C₃-alkyl, each of which is optionally mono- totrisubstituted by fluorine; represents cyclopentyl or cyclohexyl; orrepresents phenyl or benzyl, each of which is optionally monosubstitutedby fluorine, chlorine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl,methoxy, ethoxy, trifluoromethyl, or trifluoromethoxy.
 23. A compound offormula (I-1-B) according to claim 18

in which X represents phenyl that is monosubstituted by chlorine ortrifluoromethyl, Y represents methyl, Z represents methyl, A representsmethyl, B represents methyl, A, B, and the carbon atom to which they areattached represent C₆-cycloalkyl that is monosubstituted by methoxy, Drepresents hydrogen, and G represents hydrogen or the group

in which R² represents C₁-C₆-alkyl.
 24. A process for preparing acompound according to claim 18 comprising (A) for3-pyrazolylpyrrolidine-2,4-diones of formula (I-1-B-a) or enols thereof

in which A, B, D, X, Y, and Z are as defined in claim 18,intramolecularly condensing an N-acylamino acid ester of formula (II-B),

in which A, B, D, X, Y, and Z are as defined in claim 18, and R⁸represents alkyl, in the presence of a diluent and in the presence of abase, (B) for substituted 3-pyrazolyl-4-hydroxy-Δ³-dihydrofuranonederivatives of formula (I-2-A-a) or (I-2-B-a)

in which A, B, X, Y, and Z are as defined in claim 18, intramolecularlycondensing a carboxylic acid ester of formula (III-A) or (III-B),respectively,

in which A, B, X, Y, and Z are as defined in claim 18, and R⁸ representsalkyl, in the presence of a diluent and in the presence of a base, (C)for substituted 3-thiazolyl-4-hydroxy-Δ³-dihydrothiophen-2-onederivatives of formula (I-3-A-a) or (I-3-B-a)

in which A, B, X, Y, and Z are as defined in claim 18, intramolecularlycyclizing a β-ketocarboxylic acid ester of formula (IV-A) or (IV-B),respectively,

in which A, B, X, Y, and Z are as defined in claim 18, R⁸ representsalkyl, and W¹ represents hydrogen, halogen, alkyl, or alkoxy, optionallyin the presence of a diluent and in the presence of an acid, (D) forcompounds of formula (I-1-B-b), (I-2-A-b), (I-2-B-b), (I-3-A-b), or(I-3-B-b)

in which A, B, D, R¹, X, Y, and Z are as defined in claim 18, reacting acompound of formula (I-1-B-a), (I-2-A-a), (I-2-B-a), (I-3-A-a), or(I-3-B-a), respectively, (α) with an acid halide of formula (V)

in which R¹ is as defined in claim 18, and Hal represents halogen, or(β) with a carboxylic anhydride of formula (VI)R¹—CO—O—CO—R¹   (VI) in which R¹ is as defined in claim 18, optionallyin the presence of a diluent and optionally in the presence of an acidbinder, (E) for compounds of formula (I-1-B-c), (I-2-A-c), (I-2-B-c),(I-3-A-c), or (I-3-B-c)

in which A, B, D, R², M, X, Y, and Z are as defined in claim 18, and Lrepresents oxygen, reacting a compound of formula (I-1-B-a), (I-2-A-a),(I-2-B-a), (I-3-A-a), or (I-3-B-a), respectively, with a chloroformicacid ester or chloroformic acid thioester of formula (VII)R²-M-CO—Cl   (VII) in which R² and M are as defined in claim 18,optionally in the presence of a diluent and optionally in the presenceof an acid binder; (F) for compounds of formula (I-1-B-c), (I-2-A-c),(I-2-B-c), (I-3-A-c), or (I-3-B-c)

in which A, B, D, R², M, X, Y, and Z are as defined in claim 18, and Lrepresents sulphur, reacting a compound of formula (I-1-B-a), (I-2-A-a),(I-2-B-a), (I-3-A-a), or (I-3-B-a), respectively, with achloromonothioformic acid ester or chlorodithioformic acid ester offormula (VIII)

in which R² and M are as defined in claim 18, optionally in the presenceof a diluent and optionally in the presence of an acid binder; (G) forcompounds of formula (I-1-B-d), (I-2-A-d), (I-2-B-d), (1-3-A-d), or(I-3-B-d)

in which A, B, D, R³, X, Y and Z are as defined in claim 18, reacting acompound of formula (I-1-B-a), (I-2-A-a), (I-2-B-a), (I-3-A-a), or(I-3-B-a), respectively, with a sulphonyl chloride of formula (IX)R³—SO₂—Cl   (IX) in which R³ is as defined in claim 18, optionally inthe presence of a diluent and optionally in the presence of an acidbinder, (H) for compounds of formula (I-1-B-e), (I-2-A-e), (I-2-B-e),(I-3-A-e), or (I-3-B-e)

in which A, B, D, L, R⁴, R⁵, X, Y, and Z are as defined in claim 18,reacting a compound of formula (I-1-B-a), (I-2-A-a), (I-2-B-a),(I-3-A-a), or (I-3-B-a), respectively, with a phosphorus compound offormula (X)

in which L, R⁴, and R⁵ are as defined in claim 18, and p2 Hal representshalogen, optionally in the presence of a diluent and optionally in thepresence of an acid binder, (I) for compounds of formula (I-1-B-f),(I-2-A-f), (I-2-B-f), (I-3-A-f), or (I-3-B-f)

in which A, B, D, E, X, Y, and Z are as defined in claim 18, reacting acompound of formula (I-1-B-a), (I-2-A-a), (I-2-B-a), (I-3-A-a), or(I-3-B-a), respectively, with a metal compound of formula (XI)Me(OR¹⁰)_(t)   (XI) in which Me represents a mono- or divalent metal,R¹⁰ represents hydrogen or alkyl, and t represents the number 1 or 2, oran amine of formula (XII)

in which R¹⁰, R¹¹, and R¹² independently of one another representhydrogen or alkyl, optionally in the presence of a diluent, and (J) forcompounds of formula (I-1-B-g), (I-2-A-g), (I-2-B-g), (I-3-A-g), or(I-3-B-g)

in which A, B, D, L, R⁶, R⁷, X, Y and Z are as defined in claim 18,reacting a compound of formula (I-1-B-a), (I-2-A-a), (I-2-B-a),(I-3-A-a), or (I-3-B-a), respectively, (α) with an isocyanate orisothiocyanate of formula (XIII)R⁶—N═C=L   (XIII) in which R⁶ and L are as defined in claim 18,optionally in the presence of a diluent and optionally in the presenceof a catalyst, or (β) with a carbamoyl chloride or thiocarbamoylchloride of formula (XIV)

in which L, R⁶ and R⁷ are as defined in claim 18, optionally in thepresence of a diluent and optionally in the presence of an acid binder.25. A compound of formula (II-B)

in which X represents optionally substituted phenyl or hetaryl, Yrepresents hydrogen or alkyl, Z represents alkyl, halogen, hydroxyl,alkoxy, or haloalkoxy; or represents optionally substitutedphenylalkyloxy, hetarylalkyloxy, or cycloalkyl, A represents hydrogen;represents optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,polyalkoxyalkyl, or alkylthioalkyl; represents saturated or unsaturated,optionally substituted cycloalkyl in which one or more ring atom isoptionally replaced by a heteroatom; or represents optionally halogen-,alkyl-, haloalkyl-, alkoxy-, haloalkoxy-, cyano-, or nitro-substitutedaryl, arylalkyl, or hetaryl, B represents hydrogen, alkyl, oralkoxyalkyl, or A and B together with the carbon atom to which they areattached represent a saturated or unsaturated, unsubstituted orsubstituted cycle that optionally contains one or more heteroatoms, Drepresents hydrogen; represents optionally substituted alkyl, alkenyl,alkynyl, alkoxyalkyl, polyalkoxyalkyl, or alkylthioalkyl; representssaturated or unsaturated cycloalkyl in which one or more ring atoms areoptionally replaced by heteroatoms; or represents optionally substitutedarylalkyl, aryl, hetarylalkyl, or hetaryl, or A and D together with theatoms to which they are attached represent a saturated or unsaturatedcycle that is unsubstituted or substituted in the A,D moiety andoptionally contains one or more heteroatoms, and R⁸ represents alkyl.26. A compound of formula (III-A) or (III-B)

in which X represents optionally substituted phenyl or hetaryl, Yrepresents hydrogen or alkyl, Z represents alkyl, halogen, hydroxyl,alkoxy, or haloalkoxy; or represents optionally substitutedphenylalkyloxy, hetarylalkyloxy, or cycloalkyl, A represents hydrogen;represents optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,polyalkoxyalkyl, or alkylthioalkyl; represents saturated or unsaturated,optionally substituted cycloalkyl in which one or more ring atom isoptionally replaced by a heteroatom; or represents optionally halogen-,alkyl-, haloalkyl-, alkoxy-, haloalkoxy-, cyano-, or nitro-substitutedaryl, arylalkyl, or hetaryl, B represents hydrogen, alkyl, oralkoxyalkyl, or A and B together with the carbon atom to which they areattached represent a saturated or unsaturated, unsubstituted orsubstituted cycle that optionally contains one or more heteroatoms, andR⁸ represents alkyl.
 27. A compound of formula (IV-A) or (IV-B)

in which X represents optionally substituted phenyl or hetaryl, Yrepresents hydrogen or alkyl, Z represents alkyl, halogen, hydroxyl,alkoxy, or haloalkoxy; or represents optionally substitutedphenylalkyloxy, hetarylalkyloxy, or cycloalkyl, A represents hydrogen;represents optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl,polyalkoxyalkyl, or alkylthioalkyl; represents saturated or unsaturated,optionally substituted cycloalkyl in which one or more ring atom isoptionally replaced by a heteroatom; or represents optionally halogen-,alkyl-, haloalkyl-, alkoxy-, haloalkoxy-, cyano-, or nitro-substitutedaryl, arylalkyl, or hetaryl, B represents hydrogen, alkyl, oralkoxyalkyl, or A and B together with the carbon atom to which they areattached represent a saturated or unsaturated, unsubstituted orsubstituted cycle that optionally contains one or more heteroatoms, R⁸represents alkyl, and W¹ represents hydrogen, halogen, alkyl, or alkoxy.28. A compound of formula (XIX-A) or (XIX-B)

in which X represents optionally substituted phenyl or hetaryl, Yrepresents hydrogen or alkyl, and Z represents alkyl, halogen, hydroxyl,alkoxy, or haloalkoxy; or represents optionally substitutedphenylalkyloxy, hetarylalkyloxy, or cycloalkyl.
 29. A pesticidecomprising one or more compounds of formula (I) according to claim 18.30. A microbicide comprising one or more compounds of formula (I)according to claim
 18. 31. A herbicide comprising one or more compoundsof formula (I) according to claim
 18. 32. A method for controllinganimal pests comprising allowing an effective amount of a compound offormula (I) according to claim 18 to act on a pest and/or its habitat.33. A method for controlling unwanted vegetation comprising allowing aneffective amount of a compound of formula (I) according to claim 18 toact on an unwanted plant and/or its habitat.
 34. A method forcontrolling fungi comprising allowing an effective amount of a compoundof formula (I) according to claim 18 to act on a fungus and/or itshabitat.
 35. A process for preparing a pesticide, microbicide, orherbicide comprising mixing a compound of formula (I) according to claim18 with one or more extenders and/or surfactants.